CN111032633B - 3-acylbenzamides and their use as herbicides - Google Patents

3-acylbenzamides and their use as herbicides Download PDF

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CN111032633B
CN111032633B CN201880050351.XA CN201880050351A CN111032633B CN 111032633 B CN111032633 B CN 111032633B CN 201880050351 A CN201880050351 A CN 201880050351A CN 111032633 B CN111032633 B CN 111032633B
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C·沃尔德拉夫
A·科恩
H·阿伦斯
R·布劳恩
H·迪特里希
A·B·马切蒂拉
C·H·罗辛格
E·加茨魏勒
E·阿斯马斯
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract

The invention relates to 3-acyl-benzamides of formula (I) as herbicides. In the formula (I), X, Y, Z and R x Represents groups such as alkyl, cycloalkyl and halogen.

Description

3-acylbenzamides and their use as herbicides
The present invention relates to the technical field of herbicides, in particular for selectively controlling weeds and grassy weeds in crops of useful plants.
WO2012/028579A1 discloses herbicidally active phenylamides which may carry various substituents at the 3-position of the phenyl ring. WO 2017/005567 A1, EP 3 118 199 A1 and WO 2017/055146 A1 also describe herbicidally active phenylamides which may carry various substituents in the 3-position of the phenyl ring. In addition, these publications each disclose (in examples 1-364 to 1-367 and 1-426 to 1-429) a single phenylamide with an acetyl group or a cyclopropylcarbonyl group at the 3-position of the phenyl ring. However, the benzamides known from the abovementioned publications do not always have sufficient herbicidal efficacy and/or compatibility with crop plants.
It is an object of the present invention to provide alternative herbicidal active ingredients. This object is achieved by the benzamides of the invention which carry an acyl group in the 3-position of the benzene ring.
Accordingly, the present invention provides 3-acylbenzamides of formula (I)
Figure BDA0002379467770000011
Wherein the symbols and subscripts are defined as follows:
R X is represented by (C) 1 -C 6 ) -an alkyl group,
x represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) Alkyl radicals, (C) 3 -C 6 ) -cycloalkyl, R 1 O、R 2 S(O) n Or R 1 O-(C 1 -C 6 ) -an alkyl group,
y represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) -alkyl or R 1 O、R 2 S(O) n ，
Z represents (C) 1 -C 6 ) Alkyl radicals, (C) 3 -C 6 ) -cycloalkyl, (C) 2 -C 6 ) -alkenyl, (C) 3 -C 6 ) -alkynyl, halo- (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 6 ) -alkyl-O- (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 6 ) alkyl-C (O), (C) 1 -C 6 ) alkyl-C (O) - (C) 1 -C 6 ) Alkyl, phenyl or heterocyclyl, where the groups phenyl, heterocyclyl, (C) 2 -C 6 ) -alkenyl, (C) 3 -C 6 ) -alkynyl and (C) 3 -C 6 ) Cycloalkyl each bearing m substituents R 3 ，
R 1 Is represented by (C) 1 -C 6 ) -alkyl or halo- (C) 1 -C 6 ) -an alkyl group,
R 2 is represented by (C) 1 -C 6 ) -an alkyl group,
R 3 represents halogen, (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 3 ) -alkyl-O-C (O), cyano or halo- (C) 1 -C 6 ) -an alkyl group,
m represents 0, 1,2, 3 or 4,
n represents 0, 1 or 2.
In formula (I) and all subsequent formulae, the alkyl group having more than two carbon atoms may be straight-chain or branched. Alkyl radicals are, for example, methyl, ethyl, n-or isopropyl, n-butyl, isobutyl, tert-butyl or 2-butyl, pentyl, hexyl radicals such as the n-hexyl radical, isohexyl radical and 1, 3-dimethylbutyl radical. Similarly, alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. The multiple bonds may be anywhere in each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system having three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Halogen is fluorine, chlorine, bromine or iodine.
Heterocyclyl is a saturated, partially saturated or fully unsaturated cyclic group containing 3 to 6 ring atoms of which 1 to 4 are selected from oxygen, nitrogen and sulfur. For example, heterocyclyl is piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxetanyl, thienyl, and furanyl.
Depending on the nature of the substituents and their mode of attachment, the compounds of formula (I) may exist as stereoisomers. For example, if one or more asymmetrically substituted carbon atoms are present, enantiomers and diastereomers may be present. Stereoisomers likewise occur when n is 1 (sulfoxide). Stereoisomers may be obtained from the mixtures obtained by customary separation methods, for example by chromatographic separation methods. Stereoisomers can likewise be prepared selectively by using stereoselective reactions and using optically active starting materials and/or auxiliaries. The invention also relates to all stereoisomers encompassed by formula (I) but not explicitly defined and mixtures thereof.
Preferred are compounds of formula (I) wherein the symbols and subscripts are defined as follows:
R X is represented by (C) 1 -C 6 ) -an alkyl group, which is,
x represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) Alkyl radicals, (C) 3 -C 6 ) -cycloalkyl, R 1 O、R 2 S(O) n Or R 1 O-(C 1 -C 6 ) -an alkyl group,
y represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) -alkyl or R 1 O、R 2 S(O) n ，
Z represents (C) 1 -C 6 ) -alkanesBase, (C) 3 -C 6 ) -cycloalkyl, (C) 2 -C 6 ) -alkenyl, (C) 3 -C 6 ) -alkynyl, halo- (C) 1 -C 6 ) Alkyl, (C) 1 -C 6 ) -alkyl-O- (C) 1 -C 6 ) Alkyl, (C) 1 -C 6 ) alkyl-C (O), (C) 1 -C 6 ) alkyl-C (O) - (C) 1 -C 6 ) Alkyl or phenyl, where the radicals phenyl, (C) 2 -C 6 ) -alkenyl, (C) 3 -C 6 ) -alkynyl and (C) 3 -C 6 ) Cycloalkyl each bearing m substituents R 3 ，
R 1 Is represented by (C) 1 -C 6 ) -alkyl or halo- (C) 1 -C 6 ) -an alkyl group, which is,
R 2 is represented by (C) 1 -C 6 ) -an alkyl group,
R 3 represents halogen, (C) 1 -C 6 ) Alkyl, (C) 1 -C 3 ) -alkyl-O-C (O), cyano or halo- (C) 1 -C 6 ) -an alkyl group, which is,
m represents 0, 1,2, 3 or 4,
n represents 0, 1 or 2.
Particular preference is given to compounds of the formula (I) in which the symbols and indices are defined as follows:
R X is represented by (C) 1 -C 6 ) -an alkyl group,
x represents fluorine, chlorine, bromine, iodine, methyl, ethyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxymethyl, methoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylsulfanyl or ethylsulfonyl,
y represents chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, difluoromethyl, methylsulfanyl, methylsulfinyl, methylsulfonyl or ethylsulfonyl,
z represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, tert-butyl, methoxymethyl, chloromethyl, acetyl, vinyl, 1-methylvinyl, 2-methylvinyl, (1, 2-dimethyl) vinyl, (2, 2-dimethyl) vinyl, 1-methylcyclopropyl, 2-methylcyclopropyl, (2, 2-dimethyl) cyclopropyl, (1, 2-dimethyl) cyclopropyl, 2-fluorocyclopropyl, (2, 2-difluoro) cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-thienyl, 2-furyl, phenyl, 4-methoxyphenyl, 4-chlorophenyl, (3-trifluoromethyl) phenyl, 3, 5-difluorophenyl, trifluoromethyl or difluoromethyl.
In all formulae indicated below, unless defined differently, the substituents and symbols have the same meaning as described for formula (I).
The compounds of formula (II) are novel and very suitable as intermediates for the preparation of the compounds of formula (I) according to the invention. Accordingly, the present invention also provides compounds of formula (II)
Figure BDA0002379467770000031
Wherein the symbols and subscripts are defined as follows:
l represents halogen or R 4 O，
R 4 Represents hydrogen or (C) 1 -C 6 ) -an alkyl group,
X 1 represents halogen, (C) 1 -C 6 ) Alkyl radicals, (C) 3 -C 6 ) -cycloalkyl, R 1 O or R 2 S(O) n ，
Y 1 Represents a trifluoromethyl group or a difluoromethyl group,
R 1 is represented by (C) 1 -C 6 ) -alkyl or halo- (C) 1 -C 6 ) -an alkyl group,
R 2 is represented by (C) 1 -C 6 ) -an alkyl group.
Preferred are compounds of formula (II) wherein:
l represents chlorine, methoxy or hydroxy,
X 1 represents methyl, ethyl, cyclopropyl, methoxy, methylsulfanyl, ethylsulfanyl, fluorine, chlorine, bromine or iodine,
Y 1 represents a trifluoromethyl group or a difluoromethyl group,
z represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, tert-butyl, methoxymethyl, chloromethyl, acetyl, vinyl, 1-methylvinyl, 2-methylvinyl, (1, 2-dimethyl) vinyl, (2, 2-dimethyl) vinyl, 1-methylcyclopropyl, 2-methylcyclopropyl, (2, 2-dimethyl) cyclopropyl, (1, 2-dimethyl) cyclopropyl, 2-fluorocyclopropyl, (2, 2-difluoro) cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-thienyl, 2-furyl, phenyl, 4-methoxyphenyl, 4-chlorophenyl, (3-trifluoromethyl) phenyl, (3, 5-difluoro) phenyl, trifluoromethyl or difluoromethyl,
R 1 is represented by (C) 1 -C 6 ) -alkyl or halo- (C) 1 -C 6 ) -an alkyl group,
R 2 is represented by (C) 1 -C 6 ) -an alkyl group.
The compounds of formula (I) of the present invention may be prepared, for example, by the methods specified in WO2012/028579 A1. The compounds of the formula (II) required for this purpose can be synthesized using reactions known to those skilled in the art, the synthetic route used depending, inter alia, on the substitution pattern of the compounds of the formula (I) or of the formula (II). In the formulae shown in schemes 1 and 2 below, the substituents L, X 1 、Y 1 And Z each have the meaning mentioned above for the compounds of formula (II).
Scheme 1
Figure BDA0002379467770000051
The compounds of formula (II) can be prepared, for example, according to the reaction sequence given in scheme 1 (starting from substituted methyl aromatic compounds) by side chain bromination, oxidation, nucleophilic introduction of the group Z and subsequent oxidation. Substituted methyl aromatic compounds are known in principle and/or can be prepared by the process given in WO2012/028579 A1.
Scheme 2
Figure BDA0002379467770000052
The compounds of formula (II) can also be prepared, for example, by diazotization, the Sandmeyer reaction and subsequent Grignard reaction according to the reaction sequence given in scheme 2 (starting from a substituted aminoaromatic compound).
The compounds of formula (II) wherein Z represents cyclopropyl may also be prepared from compounds of formula (II) wherein Z represents vinyl, by cyclopropanation with, for example, diazomethane or trimethyl sulphoxide halides.
The collection of compounds of formula (I) which can be synthesized by the above reaction can also be prepared in parallel, in which case it can be done manually, semi-automatically or fully automatically. For example, the reaction, work-up or purification of the products and/or intermediates can be automated. In general, this is understood to mean, for example, the process described by D.Tiebes in composite Chemistry-Synthesis (ed: kunther Jung), wiley,1999, pages 1 to 34.
For reactions and work-up carried out in parallel, a number of commercially available devices can be used, for example the Calypso reaction module from Barnstead International, dubuque, iowa 52004-0797, USA or the reaction stations from Radleys, shirehill, saffron Walden, essex, CB11 3AZ, england, or the MultiPROBE automation workstation from Perkin Elmer, waltham, massachusetts 02451, USA. For parallel purification of compounds of formula (I) or intermediates occurring during the preparation, useful instruments include chromatographic instruments, such as those from ISCO, inc.,4700Superior street, lincoln, ne 68504, usa.
The instrument creates a modular program in which the individual work steps are automated, but manual operations must be performed between work steps. This can be avoided by using a partially or fully integrated automation system, wherein the individual automation modules are, for example, handled by a robot. Automated systems of this type are available, for example, from Caliper, hopkinton, MA 01748, usa.
The performance of a single or multiple synthetic steps may be aided by the use of polymer-supported reagents/scavenging resins. The technical literature describes a series of protocols, for example in ChemFiles, vol.4, no. 1, polymer-Supported scanners and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).
In addition to the methods described herein, the compounds of formula (I) may be prepared in whole or in part by solid phase supported methods. To this end, individual intermediates or all intermediates in the synthesis or in the synthesis suitable for the respective process are bound to the synthetic resin. Solid phase supported Synthesis methods are described in detail in The technical literature, for example, barry A. Bunin in "The Combinatorial Index", academic Press,1998 and Combinatorial Chemistry-Synthesis, analysis, screening (ed.: kurther Jung), wiley, 1999. Various protocols are carried out using solid-phase supported synthetic methods, which are known in the literature and which can themselves also be carried out manually or by automated means. The reaction can be carried out, for example, by means of the IRORI technique in microreactors available from Nexus Biosystems,12140Community road, poway, CA92064, USA.
In both solid and liquid phases, the performance of a single or multiple synthetic steps can be assisted by the use of microwave techniques. A series of experimental protocols are described in the specialist literature, for example in Microwaves in Organic and Medicinal Chemistry (ed: C.O.kappa.and A.Stadler), wiley, 2005.
The preparation by the method described herein gives compounds of formula (I) in the form of a collection of substances, which are called libraries (libraries). The invention also provides libraries comprising at least two compounds of formula (I).
The compounds of the present invention have excellent herbicidal efficacy against a broad spectrum of economically important annual monocotyledonous and dicotyledonous harmful plants. The active ingredient is also effective against perennial weeds that germinate from rhizomes, rhizomes and other perennial organs and are difficult to control.
The present invention therefore also provides a method for controlling undesired plants or for regulating plant growth, preferably in plant crops, in which one or more compounds according to the invention are applied to the plant (for example to harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), to the seed (for example to cereals, seeds or vegetative propagules such as tubers or germinated seedling parts), or to the area in which the plant is growing (for example to the planting area). The compounds according to the invention can be applied, for example, before sowing (if appropriate also by incorporation into the soil), before emergence or after emergence. Some representative specific examples of monocotyledonous and dicotyledonous weed populations that can be controlled by the compounds of the present invention are as follows, but the list is not intended to be limited to a particular genus species:
monocotyledonous harmful plants of the following genera: aegilops (aegiops), agropyron (Agropyron), agrostis (Agrostis), alopecurus (Alopecurus), pseudoagrostis (Apera), avena (Avena), brachiaria (Brachiaria), bromus (broomus), tribulus (centchrus), commelina (Commelina), bermuda (Cynodon), sedge (cypress), cogongrass (Dactyloctenium), digitaria (Digitaria), barnyard (Echinochloa), eleocharis (Eleocharis), eleutherosis (Eleusine), teosine (Eleusine), teff (Agrostis) the genera Vietnam (Eriochloa), festuca (Festuca), fimbristylis (Fimbristylis), heterophylla (Heteranthea), imperata (Imperata), duckbill (Ischaemum), euphorbia (Leptochloa), lolium (Lolium), potentilla (Monochoria), panicum (Panicum), paspalum (Paspalum), phalaris (Phalaris), gracilaria (Phleum), poa (Poa), rottboellia (Rottboellia), sagitaria (Sagittaria), scirpus (Scirpus), setaria (Setaria), sorghum (Sorghumm).
Dicotyledonous weeds of the following genera: abutilon (Abutilon), amaranthus (Amaranthus), ambrosia (Ambrosia), monogynia (Andoa), chrysanthemum (Anthemis), rosa (Aphanes), artemisia (Artemisia), atriplex (Atriplex), bellis (Bellis), coprinus (Bidens), capsella (Capsella), carduus (Carduus), cassia (Cassia), centaurea (Centaurea), chenopodium (Chenopodium), cirsium (Cirsium), convolvulus (Convolvulus), mandaria (Datura), desmodium (Desmodium), rumex (Emex), glycine (Erysimum), euphorbia (Phorbia), weasel (Galeopsis) achyranthes (galinoga), rataria (Galium), hibiscus (Hibiscus), ipomoea (Ipomoea), kochia (Kochia), episesa (Lamium), striga (Lepidium), matricaria (Lindernia), matricaria (Matricaria), mentha (Mentha), lonicera (Mercurialis), setaria (mulluugo), myosotis (myonotis), poppy (myosponotus), papaver (Papaver), pharis (Pharbitis), plantago (Plantago), polygonum (Polygonum), portulaca (Portulaca), ranopharia (Ranunculus), raphanus (raphus), rorippa (Rorippa), arthrifolia (Rotala), rumex (Rumex), rumex (ruma), ruma (Rotala), rumex (Rumex) Salsola (Salsola), senecio (Senecio), sesbania (Sesbania), sida (Sida), sinapis (Sinapis), solanum (Solanum), endive (Sonchus), cuspidoea (sphaclean), chickweed (Stellaria), taraxacum (Taraxacum), pennycress (Thlaspi), clover (Trifolium), nettle (Urtica), veronica (Veronica), viola (Viola), xanthium (Xanthium).
If the compounds of the present invention are applied to the soil surface before germination, the germination of weed seedlings, or the weed growth reaches the cotyledonary stage, can be completely prevented, but then its growth stops and eventually dies completely after three to four weeks.
If the active ingredient is applied post-emergence to the green parts of the plants, the growth is stopped after the treatment and the weed plants remain in the growth phase at the time of the application, or they die completely after a certain time, so that in this way competition by weeds which are harmful to the crop plants can be eliminated very early and in a lasting manner.
Although the compounds of the invention exhibit significant herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crop plants, such as dicotyledonous crop plants of the following genera, are damaged only to a negligible extent, if at all, depending on the structure of the particular compounds of the invention and their application rates: arachis (Arachis), beta (Beta), brassica (Brassica), cucumis (Cucumis), cucurbita (Cucurbita), helianthus (Helianthus), daucus (Daucus), glycine (Glycine), gossypium (Gossypium), ipomoea (Ipomoea), lactuca (Lactuca), linum (Linum), lycopersicon (Lycopersicon), miscanthus (Miscanthus), nicotiana (Nicotiana), phaseolus (Phaseolus), pisum (Pisum), solanum (Solanum), vicia, or a monocotyledonous crop of the following genera: allium (Allium), ananas (Ananas), asparagus (Asparagus), avena (Avena), hordeum (Hordeum), oryza (Oryza), panicum (Panicum), saccharum (Saccharum), secale (Secale), sorghum (Sorghum), triticale (Triticale), triticum (Triticum), zea (zea), in particular zea and Triticum. For this reason, the compounds according to the invention are very suitable for selectively controlling unwanted plant growth in plant crops, for example in agriculturally useful plants or ornamentals.
In addition, the compounds of the present invention (depending on the specific chemical structure and application rate employed) have significant growth regulating properties on crop plants. They interfere with the metabolism of the plant itself by regulation and can therefore be used to influence plant constituents in a controlled manner and to promote harvesting, for example by triggering dehydration and stunting growth. In addition, they are also suitable for general control and inhibition of unwanted vegetative growth without killing the plants. Inhibition of vegetative growth has an important effect on many monocotyledonous and dicotyledonous crops, since this can reduce or completely prevent lodging, for example.
Owing to their herbicidal and plant growth-regulating properties, the active ingredients can also be used for controlling harmful plants in genetically modified plant crops or plants modified by conventional mutagenesis. In general, transgenic plants are characterized by particularly advantageous properties, for example by resistance to certain pesticides, in particular certain herbicides, by resistance to plant diseases or to pathogens of plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or viruses. Other specific characteristics relate, for example, to yield, quality, storability, composition and specific ingredients of the harvested material. For example, transgenic plants with increased starch content or altered starch quality, or those with different fatty acid compositions in the harvested material, are known.
The compounds according to the invention are preferably used in transgenic crops of economically important useful and ornamental plants, for example cereals such as wheat, barley, rye, oats, millet/sorghum, rice and maize, or else the following crops: sugar beet, cotton, soybean, oilseed rape, potato, tapioca, tomato, pea and other vegetables.
Preferably, the compounds of the invention can be used as herbicides in crops of useful plants which are resistant to the phytotoxic action of the herbicide or have been made resistant by genetic engineering.
Conventional methods for producing new plants with improved properties compared to existing plants include, for example, conventional breeding methods and mutant production methods. Alternatively, new plants with improved properties can be produced by means of recombinant methods (see, for example, EP-A-0221044, EP-A-0131624). For example, the following are described:
genetically modifying crop plants in order to modify the starch synthesized in the plant (e.g.WO 92/11376, WO 92/14827, WO 91/19806),
transgenic crop plants which are resistant to certain glufosinate herbicides (see, for example, EP-A-0242236, EP-A-242246) or glyphosate herbicides (WO 92/00377) or sulfonylurese:Sup>A herbicides (EP-A-0257993, US-A-5013659),
transgenic crop plants, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) and thus render the plants resistant to particular pests (EP-A-0142924, EP-A-0193259),
-transgenic crop plants with altered fatty acid composition (WO 91/13972),
genetically modified crop plants having novel constituents or secondary metabolites which lead to an increased disease resistance, for example novel phytoalexins (EP 309862, EPA 0464461),
genetically modified plants with reduced photorespiration, with higher yield and higher stress tolerance (EP 0305398),
transgenic crop plants producing pharmaceutically or diagnostically important proteins ("molecular farming"),
-transgenic crop plants characterized by higher yield or better quality,
transgenic crop plants characterized by combinations of novel properties such as those described above ("gene stacking").
A number of molecular biological techniques which can be used to generate novel transgenic plants with improved properties are known in principle; see, e.g., I.Potrykus and G.Spandenberg (eds.), gene Transfer to Plants, springer Lab Manual (1995), springer Verlag Berlin, heidelberg or Christou, "Trends in Plant Science"1 (1996) 423-431).
For such recombination procedures, nucleic acid molecules capable of undergoing mutagenesis or sequence change by recombination of DNA sequences can be introduced into plasmids. For example, base exchanges, partial sequence removal, or addition of natural or synthetic sequences can be performed by standard methods. To ligate the DNA fragments to each other, an adapter (adapter) or linker (linker) may be placed on the fragments; see, for example, sambrook et al, 1989, molecular cloning, A Laboratory Manual, 2 nd edition, cold Spring Harbor Laboratory Press, cold Spring Harbor, NY, or Winnacker "Gene und Klone" [ Genes and clones ], VCH Weinheim, 2 nd edition, 1996.
For example, the production of plant cells with reduced activity of a gene product can be achieved by: by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect, or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the above-mentioned gene products. For this purpose, it is possible first to use DNA molecules which comprise the complete coding sequence of the gene product, including any flanking sequences which may be present, but also DNA molecules which comprise only part of the coding sequence, in which case these part of the coding sequence must be sufficiently long to produce an antisense effect in the cell. DNA sequences having high homology to, but not identical to, the coding sequence of the gene product may also be used.
When expressing a nucleic acid molecule in a plant, the protein synthesized may be located in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, the coding region may, for example, be linked to a DNA sequence which ensures localization in a particular compartment. Such sequences are known to those skilled in the art (see, e.g., braun et al, EMBO J.11 (1992), 3219-3227, wolter et al, proc. Natl.Acad. Sci.USA 85 (1988), 846-850, sonnewald et al, plant J.1 (1991), 95-106. The nucleic acid molecule may also be expressed in an organelle of the plant cell.
The transgenic plant cells can be regenerated by known techniques to produce whole plants. In principle, the transgenic plant can be a plant of any desired plant species, i.e. not only monocotyledonous but also dicotyledonous plants.
Thus, transgenic plants with altered characteristics can be obtained by overexpressing, repressing (repressing) or suppressing homologous (= native) genes or gene sequences, or expressing heterologous (= foreign) genes or gene sequences.
The compounds of the invention can preferably be used in transgenic crops which are resistant to growth regulators, such as dicamba (dicamba), or to herbicides which inhibit essential plant enzymes, such as acetolactate synthase (ALS), EPSP synthase, glutamine Synthase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD), or to herbicides selected from sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and similar active ingredients.
When the active ingredients according to the invention are used in transgenic crops, not only the effects on harmful plants observed in other crops, but also in general a specific effect on the application in the particular transgenic crop, such as a modified or in particular broadened spectrum of preventable weeds, modified application rates which can be used for application, preferably good compatibility with the herbicides to which the transgenic crop is resistant, and an influence on the growth and yield of the transgenic crop plants, occur.
The present invention therefore also provides for the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
The compounds of the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. Accordingly, the present invention also provides herbicidal and plant growth regulating compositions comprising the compounds of the present invention.
The compounds of the present invention may be formulated in a variety of ways depending on the desired biological and/or physicochemical parameters. Possible dosage forms include, for example: wettable Powders (WP), water-Soluble Powders (SP), water-soluble concentrates, emulsifiable Concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension Concentrates (SC), oil-or water-based dispersions, oil-miscible water-soluble solutions, capsule Suspensions (CS), dusting agents (DP), seed dressings, granules for spreading and soil application, granules in the form of microparticles (GR), spray granules, adsorbents and adsorbent granules, water-dispersible granules (WG), water-Soluble Granules (SG), ULV formulations, microcapsules and waxes.
These individual formulation types are known in principle and are described, for example, in: winnacker-kuchler, "Chemische Technology" [ Chemical Technology ], volume 7, c.hauser Verlag Munich, 4 th edition, 1986; wade van Valkenburg, "Pesticide Formulations," Marcel Dekker, n.y.,1973; martens, "Spray Drying" Handbook, 3 rd edition, 1979, g.
The required formulation auxiliaries, such as inerts, surfactants, solvents and other additives, are likewise known and are described, for example, in: watkins, "Handbook of Instrument Dual ingredients and Cariers", second edition, darland Books, caldwell N.J.; olphen, "Introduction to Clay Colloid Chemistry"; second edition, j.wiley&Sons, n.y.; c. marsden, "solutions Guide", second edition, interscience, n.y.1963; mcCutcheon's "Detergents and Emulsifiers Annual", MC publishing.corp., ridgewood n.j.; sisley and Wood, "Encyclopedia of Surface Active Agents", chem.pub.Co.Inc., N.Y.1964;
Figure BDA0002379467770000121
Figure BDA0002379467770000122
[Interface-active Ethylene Oxide Adducts],Wiss.Verlagsgesellchaft.,Stuttgart 1976；Winnacker-Küchler,"Chemische Technologie[Chemical Engineering]", volume 7, c.hanser Verlag Munich, fourth edition, 1986.
Wettable powders are preparations which can be homogeneously dispersed in water and which, in addition to the active ingredient and a diluent or inert substance, comprise ionic and/or nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylbenzene sulfonates, sodium lignosulfonates, sodium 2,2 '-dinaphthylmethane-6, 6' -disulfonates, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurates. To prepare wettable powders, the active herbicidal ingredients are, for example, finely ground in conventional apparatus such as hammer mills, air-blast mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.
The emulsifiable concentrate was prepared by the following procedure: the active ingredient is dissolved in an organic solvent (for example butanol, cyclohexanone, dimethylformamide, xylene or relatively high-boiling aromatics or hydrocarbons) or a mixture of organic solvents, and one or more ionic and/or nonionic surfactants (emulsifiers) are added. Examples of emulsifiers that can be used are calcium alkylaryl sulfonates such as calcium dodecylbenzene sulfonate; or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensates, alkyl polyethers, sorbitan esters (e.g. sorbitan fatty acid esters) or polyoxyethylene sorbitan esters (e.g. polyoxyethylene sorbitan fatty acid esters).
Dusting agents are obtained by grinding the active ingredient with finely divided solids, such as talc, natural clays (e.g. kaolin, bentonite and pyrophyllite) or diatomaceous earth.
Suspension concentrates may be water-based or oil-based. They can be prepared by: for example, wet milling is carried out by commercially available ball mills, and optionally surfactants such as those listed above for the other dosage forms are added.
Emulsions, such as oil-in-water Emulsions (EW), may be prepared by: for example, by means of a stirrer, colloid mill and/or static mixer, an aqueous organic solvent and optionally a surfactant such as those listed above for the other dosage forms are used.
Granules can be prepared by spraying the active ingredient onto an absorbent particulate inert material or by applying a concentrate of the active ingredient to the surface of a carrier (e.g. sand, kaolin or particulate inert material) with the aid of a binder (e.g. polyvinyl alcohol, sodium polyacrylate or mineral oil). Suitable active ingredients may also be granulated in the conventional manner for the preparation of fertilizer granules-if desired mixed with fertilizers.
Water dispersible granules are generally prepared by conventional methods such as spray drying, fluid bed granulation, pan granulation, mixing using high speed mixers, and extrusion without solid inert materials.
For pan granulation, fluid bed granulation, extrusion granulation and spray granulation see, for example: "Spray-Drying Handbook", third edition, 1979, G.Goodwin Ltd., london, J.E.Brown, "agglomerization", chemical and Engineering 1967, page 147 and hereafter; "Perry's Chemical Engineer's Handbook", 5 th edition, mcGraw-Hill, new York 1973, pages 8-57.
For further details on the formulation of crop protection compositions, see, e.g., g.c. klingman, "Weed Control as a Science", john Wiley and Sons, inc., new York,1961, pages 81-96; freyer, S.A.Evans, "Weed Control Handbook", 5 th edition, blackwell Scientific Publications, oxford,1968, pages 101-103.
Agrochemical formulations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compounds according to the invention.
In wettable powders, the concentration of the active ingredient is, for example, about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents. In emulsifiable concentrates, the active ingredient concentration may be about 1 to 90% by weight, preferably 5 to 80% by weight. Formulations in powder form contain 1 to 30% by weight of active ingredient, preferably 5 to 20% by weight; sprayable solutions contain from about 0.05 to 80%, preferably 2 to 50% by weight of the active ingredient. In the case of water-dispersible granules, the content of active ingredient depends in part on whether the active compound is in liquid or solid form, and what granulation auxiliaries, fillers, etc. are used. In the water-dispersible granules, the content of active ingredient is, for example, 1 to 95% by weight, preferably 10 to 80% by weight.
In addition, the active ingredient formulations mentioned optionally contain various conventional binders, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, antifoams, evaporation inhibitors and agents which influence the pH and viscosity.
On the basis of these formulations, it is also possible to prepare combinations with other insecticidal active substances, for example insecticides, acaricides, herbicides, fungicides and also safeners, fertilizers and/or growth regulators, for example in the form of finished preparations or tank mixes.
For application, the formulations in the form as marketed are, if appropriate, diluted in a customary manner, such as with water in the case of wettable powders, emulsifiable concentrates, dispersants and water-dispersible granules. Dusts, granules for soil application, granules for spreading and sprayable solutions are usually not further diluted with other inert substances before application.
The desired application rate of the compounds of the formula (I) varies with the external conditions, including, inter alia, temperature, humidity and the type of herbicide used. The application rate can vary within wide limits, for example from 0.001 to 1.0kg/ha or more of active substance, however, preferably from 0.005 to 750kg/ha.
The following examples illustrate the invention.
Chemical examples
Preparation of the Compound of formula (II)
Example 1: preparation of methyl 3-acetyl-2-chloro-4- (trifluoromethyl) benzoate (example Nos. 4 to 99)
Methyl 3-acetyl-2-chloro-4- (trifluoromethyl) benzoate was prepared according to the following scheme:
Figure BDA0002379467770000151
step 1: preparation of 2-chloro-3-methyl-4- (trifluoromethyl) benzoic acid (IV).
75g (324 mmol) of 2-amino-3-methyl-4- (trifluoromethyl) benzoic acid (III) (CAS 1508551-20-9) are initially added to a mixture of 350mL of water and 370mL of concentrated hydrochloric acid. 24.79g (359 mmol) of sodium nitrite (dissolved in 100mL of water) are added dropwise at 0-5 ℃. Additionally, 50.81g (513 mmol) of copper (I) chloride were dissolved in 150mL of water and 200mL of concentrated hydrochloric acid, and the mixture was heated to 60 ℃. At this temperature, the diazonium salt mixture is added dropwise. The resulting reaction mixture was stirred at 60 ℃ for 2 hours and at Room Temperature (RT) overnight. The mixture was then cooled to 0 ℃ and the precipitate was filtered off. The precipitate is washed with water and dried at 150mbar and 40 ℃ for 12 hours. 76.4g of 2-chloro-3-methyl-4- (trifluoromethyl) benzoic acid (IV) were obtained.
Step 2: preparation of methyl 2-chloro-3-methyl-4- (trifluoromethyl) benzoate (V).
60.1g (252 mmol) of 2-chloro-3-methyl-4- (trifluoromethyl) benzoic acid (IV) are initially taken in 590mL of methanol and 80.56mL (1.51 mol) of sulfuric acid are added at room temperature. The mixture was stirred at reflux for 2 hours. The mixture was then cooled to room temperature and the volatile components were removed under reduced pressure. The residue was dissolved in water and extracted with dichloromethane. The organic phase was dried and concentrated under reduced pressure. The residue was purified by chromatography (ethyl acetate/n-heptane). 89.67g of methyl 2-chloro-3-methyl-4- (trifluoromethyl) benzoate (V) were obtained.
And step 3: preparation of methyl 3- (bromomethyl) -2-chloro-4- (trifluoromethyl) benzoate (VI).
62.4g (247 mmol) of methyl 2-chloro-3-methyl-4- (trifluoromethyl) benzoate (V) are suspended in 640mL of chlorobenzene and 52.7g (296 mmol) of N-bromosuccinimide and 406mg (2.47 mmol) of AIBN are added. The mixture was warmed to 60 ℃, 0.64mL (12.35 mmol) bromine was added and the mixture was heated to 110 ℃. After stirring at this temperature for 12 hours, 20g of N-bromosuccinimide and 120. Mu.L of bromine were further added, and the mixture was stirred at 110 ℃ for another 6 hours. After cooling to room temperature, the reaction mixture was washed with an aqueous solution of sodium thiosulfate. Separating the organic phase from the CH 2 Cl 2 The aqueous phase was washed (dichloromethane). The combined organic phases were dried and concentrated. The residue was purified by chromatography (B)Ethyl acetate/n-heptane). 77.1g of methyl 3- (bromomethyl) -2-chloro-4- (trifluoromethyl) benzoate (VI) are obtained.
And 4, step 4: preparation of methyl 2-chloro-3-formyl-4- (trifluoromethyl) benzoate (VII).
68.4g (266 mmol) of methyl 3- (bromomethyl) -2-chloro-4- (trifluoromethyl) benzoate (VI) are initially introduced into 500mL of acetonitrile and 7.25g (619 mmol) of N-methylmorpholine N-oxide are added. After stirring at room temperature for 6 hours, the mixture was concentrated and the residue was dissolved in ethyl acetate and washed twice with water. The organic phase was dried and concentrated. Chromatography (ethyl acetate/n-heptane) gave 49.5g of methyl 2-chloro-3-formyl-4- (trifluoromethyl) benzoate (VII).
And 5: preparation of methyl 2-chloro-3- (1-hydroxyethyl) -4- (trifluoromethyl) benzoate (VIII).
3g (11 mmol) of methyl 2-chloro-3-formyl-4- (trifluoromethyl) benzoate (VII) were initially introduced into 20mL of anhydrous THF (tetrahydrofuran) and a solution of 3.97mL (14 mmol) of methylmagnesium bromide in THF was carefully added at-70 ℃. The cooling was then removed and the mixture was stirred at room temperature for 12 hours. The mixture was then added to 2 moles of hydrochloric acid and used with CH 2 Cl 2 And (4) extracting. The organic phase was dried and concentrated. Chromatography (ethyl acetate/n-heptane) afforded methyl 2-chloro-3- (1-hydroxyethyl) -4- (trifluoromethyl) benzoate (VIII). 1 H-NMR(400MHz,DMSO-d 6 ):δ＝7.81(d,1H)；7.71(d,1H)；5.60(d,1H)；5.32(m,1H)；3.90(s,3H)；1.51(d,3H)。
Step 6: preparation of methyl 3-acetyl-2-chloro-4- (trifluoromethyl) benzoate.
1.44g (14 mmol) of chromium (VI) oxide are added to 1.47mL of concentrated sulfuric acid at 0 ℃ and the mixture is added dropwise to 10mL of water at 0 ℃. Then 3.4g (12 mmol) of methyl 2-chloro-3- (1-hydroxyethyl) -4- (trifluoromethyl) benzoate (VIII) dissolved in 23mL of acetone were added dropwise at 0 ℃. The mixture was warmed to room temperature and stirred for a further 3 hours. The reaction was then quenched with isopropanol, acetone and isopropanol were removed by distillation, and the residue was extracted with ethyl acetate. The organic phase was dried and concentrated. 2.66g of methyl 3-acetyl-2-chloro-4- (trifluoromethyl) benzoate are obtained.
Example 2: preparation of methyl 3- (cyclopropylcarbonyl) -2-methyl-4- (trifluoromethyl) benzoate (example Nos. 4 to 5).
Step 1: preparation of methyl 3-iodo-2-methyl-4- (trifluoromethyl) benzoate
40g (172 mmol) of methyl 3-amino-2-methyl-4- (trifluoromethyl) benzoate (CAS 2092141-87-0) are dissolved in 400mL of concentrated hydrochloric acid, and the mixture is cooled to 0-5 ℃ and stirred for 20 minutes. A solution of 13g (189 mmol) of sodium nitrite in 60mL of water is then slowly added dropwise and the mixture is stirred at 0-5 ℃ for 2 hours. 4.1g (69 mmol) of urea are added and after a further 10 minutes of stirring a solution of 42.7g (257 mmol) of potassium iodide in 30mL of water is also added dropwise at 0 to 5 ℃. The reaction mixture was then warmed to room temperature, poured into 400mL of ice water, and charged with CH 2 Cl 2 And (4) extracting. The organic phase was washed with saturated aqueous sodium thiosulfate, dried and concentrated. The residue was purified by chromatography (ethyl acetate/n-heptane). 51.4g of methyl 3-iodo-2-methyl-4- (trifluoromethyl) benzoate were obtained.
Step 2: preparation of methyl 3- (cyclopropylcarbonyl) -2-methyl-4- (trifluoromethyl) benzoate.
5g (13.7 mmol) of methyl 3-iodo-2-methyl-4- (trifluoromethyl) benzoate were first added to 20mL of dry THF, and 13.7mL of a 1.3 molar (17.8 mmol) solution of isopropylmagnesium chloride/lithium chloride in THF were added at-30 deg.C, and the mixture was stirred at-30 deg.C for 1 hour. Again at-30 ℃ 4.23g (27.4 mmol) of cyclopropanecarboxylic anhydride are then added dropwise. The resulting mixture was allowed to warm to room temperature over 2 hours. THF is removed by distillation and the residue is dissolved in water and a small amount of 2 mol hydrochloric acid and treated with CH 2 Cl 2 And (4) extracting. The organic phase was dried and concentrated. Purification by chromatography (ethyl acetate/n-heptane) gave 3.6g of methyl 3- (cyclopropylcarbonyl) -2-methyl-4- (trifluoromethyl) benzoate.
Preparation of Compounds of formula (I)
Example 1: preparation of 3-acetyl-2-chloro-N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide (example Nos. 1-137)
150mg (0.56 mmol) of 3-acetyl-2-chloro-4- (trifluoromethyl) benzoic acid and 74mg (0.73 mmol) of 1-methyl-1H-tetrazol-5-amine in 5mL CH 2 Cl 2 To this solution, 0.5mL (0.84 mmol) of a 50% strength solution of propanephosphonic anhydride in THF was added at room temperature. The mixture was stirred for 1 hour, then 0.4mL triethylamine and a catalytic amount of DMAP were added. The mixture was then stirred at room temperature for a further 3 hours, followed by addition of 5mL of 2N hydrochloric acid, 5mL of water and 5mL of CH 2 Cl 2 And the mixture was stirred for 10 minutes. The organic phase was separated off and concentrated. Purification by chromatography (acetonitrile/water +0.5% trifluoroacetic acid) gave 110mg of 3-acetyl-2-chloro-N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide.
Example 2: preparation of 3-acetyl-2-chloro-N- (1-ethyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide (example Nos. 2-137)
200mg (0.75 mmol) of 3-acetyl-2-chloro-4- (trifluoromethyl) benzoic acid are initially introduced into 3mL of pyridine and 107mg (0.9 mmol) of 1-ethyl-1H-tetrazol-5-amine are added. Then 0.1mg (1.14 mmol) of oxalyl chloride was added and the mixture was stirred at room temperature for 12 hours. 5mL of water were then added, the mixture was stirred for a further 10 minutes with CH 2 Cl 2 And (4) extracting. The organic phase is separated off, dried and concentrated by evaporation. Chromatography (acetonitrile/water +0.5% trifluoroacetic acid) afforded 66mg of 3-acetyl-2-chloro-N- (1-ethyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide.
Example 3: preparation of 3- (cyclopropylcarbonyl) -2-methyl-N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide (example Nos. 1 to 18)
In analogy to example 2, from 240mg (0.88 mmol) of 3- (cyclopropylcarbonyl) -2-methyl-4- (trifluoromethyl) benzoic acid and 107mg (1.05 mmol) of 1-methyl-1H-tetrazol-5-amine was obtained 196mg of 3- (cyclopropylcarbonyl) -2-methyl-N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide.
Example 4: preparation of 3- (cyclopropylcarbonyl) -N- (1-ethyl-1H-tetrazol-5-yl) -2-methyl-4- (trifluoromethyl) benzamide (example Nos. 2 to 18)
Similarly, from 155mg (0.56 mmol) of 3- (cyclopropylcarbonyl) -2-methyl-4- (trifluoromethyl) benzoic acid and 81mg (0.68 mmol) of 1-ethyl-1H-tetrazol-5-amine, 95mg of 3- (cyclopropylcarbonyl) -N- (1-ethyl-1H-tetrazol-5-yl) -2-methyl-4- (trifluoromethyl) benzamide were obtained.
The examples listed in the following table are prepared or can be obtained analogously to the above-described process. These compounds are very particularly preferred.
Abbreviations used indicate:
ph = phenyl Me = methyl Et = ethyl c-Pr = cyclopropyl
Bu = butyl i-Pr = isopropyl
Table 1: wherein R is x Compounds of the formula (I) according to the invention which represent methyl and the other substituents have the following meanings.
Figure BDA0002379467770000191
Figure BDA0002379467770000192
Figure BDA0002379467770000201
Figure BDA0002379467770000211
Figure BDA0002379467770000221
Figure BDA0002379467770000231
Figure BDA0002379467770000241
Figure BDA0002379467770000251
Figure BDA0002379467770000261
Figure BDA0002379467770000271
Table 2: wherein R is x Compounds of the formula (I) according to the invention which represent ethyl and the other substituents have the following meanings.
Figure BDA0002379467770000272
Figure BDA0002379467770000273
Figure BDA0002379467770000281
Figure BDA0002379467770000291
Figure BDA0002379467770000301
Figure BDA0002379467770000311
Figure BDA0002379467770000321
Figure BDA0002379467770000331
Figure BDA0002379467770000341
Table 3: wherein R is x Compounds of the formula (I) according to the invention which represent propyl and the other substituents have the following meanings.
Figure BDA0002379467770000342
Figure BDA0002379467770000351
Figure BDA0002379467770000361
Figure BDA0002379467770000371
Figure BDA0002379467770000381
Figure BDA0002379467770000391
Figure BDA0002379467770000401
Figure BDA0002379467770000411
Figure BDA0002379467770000421
Table 4: compounds of the formula (II) according to the invention in which L represents methoxy and the other substituents have the following meanings.
Figure BDA0002379467770000422
Figure BDA0002379467770000423
Figure BDA0002379467770000431
Figure BDA0002379467770000441
Figure BDA0002379467770000451
Figure BDA0002379467770000461
Figure BDA0002379467770000471
Figure BDA0002379467770000481
Table 5: compounds of the formula (II) according to the invention in which L represents hydroxy and the other substituents have the following meanings.
Figure BDA0002379467770000482
Figure BDA0002379467770000483
Figure BDA0002379467770000491
Figure BDA0002379467770000501
Figure BDA0002379467770000511
Figure BDA0002379467770000521
Figure BDA0002379467770000531
Table 6: compounds of the formula (II) according to the invention in which L represents chlorine and the other substituents have the meanings indicated below.
Figure BDA0002379467770000532
Figure BDA0002379467770000533
Figure BDA0002379467770000541
Figure BDA0002379467770000551
Figure BDA0002379467770000561
Figure BDA0002379467770000571
Figure BDA0002379467770000581
The NMR data for a number of compounds of formula (I) of the present invention mentioned in the above table are disclosed below using the NMR peak list method. Here, selected examples of 1 H-NMR data of 1 The H-NMR peak list is shown in a form. For each signal peak, the δ values in ppm are listed first, followed by the signal intensities in parentheses. The delta value-signal intensity number pairs for different signal peaks are listed spaced from each other by a semicolon. Thus, the peak list of one example has the following form:
δ 1 (intensity) 1 )；δ 2 (strength) 2 )；......；δ i (strength) i )；......；δ n (strength) n )
In the printed example of the NMR spectrum, the intensity of the spike is highly correlated with the signal in centimeters and shows a true proportion of the signal intensity. For a broad peak signal, several peaks or intermediate signals may be displayed along with their relative intensities compared to the strongest signal in the spectrum. 1 List of H NMR peaks is similar to conventional 1 H NMR prints, which therefore typically contain all the peaks listed in conventional NMR analyses. Otherwise, as is conventional 1 H NMR prints which may show peaks of solvent signal, of stereoisomers of the target compound (which are also provided by the present invention), and/or impurities.
When recording compound signals in the delta range of solvents and/or water, our 1 Tabulation of H NMR peaks showing standard solvent peaks, e.g. in DMSO-D 6 The peak with medium DMSO and the peak with water, which generally have an average higher intensity.
The peaks of stereoisomers of the compounds of the invention and/or of impurities typically have an average lower intensity than the peaks of the compounds of the invention (e.g. with a purity of > 90%).
Such stereoisomers and/or impurities may be unique to a particular method of preparation. Thus, by reference to "by-product fingerprints," their peaks can help identify the reproducibility of our manufacturing process.
If desired, a practitioner who calculates the peaks of the target compound by known methods (MestreC, ACD simulation, and empirically evaluated expected values) may optionally use additional intensity filters to isolate the peaks of the compounds of the invention. This separation is in accordance with conventional 1 The peak extractions discussed in the H NMR analyses were similar.
Examples nos. 1 to 1: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.48(br s,1H)；7.58(d,1H)；7.25(d,1H)；3.97(s,3H)；2.50(s,3H)；2.27(s,3H),2.24(s,3H)；
examples nos. 1 to 3: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.49(br s,1H)；7.59(d,1H)；7.27(d,1H)；3.97(s,3H)；2.30(s,3H)；2.26(s,3H)；2.25(m,1H)；1.15(m,4H)；
examples nos. 1 to 7: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.81(br s,1H)；7.97(d,1H)；7.93(d,1H)；4.01(s,3H)；3.22(s,3H)；2.59(s,3H)；2.35(s,3H)；
examples nos. 1 to 9: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.84(br s,1H)；7.96(d,1H)；7.91(d,1H)；3.99(s,3H)；3.21(s,3H)；2.41(s,3H)；2.36(m,1H)；1.22(m,4H)；
examples nos. 1 to 14: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.79(br s,1H)；7.88(d,1H)；7.83(d,1H)；4.01(s,3H)；2.57(s,3H)；2.34(s,3H)；
examples nos. 1 to 15: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.77(br s,1H)；7.89(d,1H)；7.83(d,1H)；4.01(s,3H)；2.85(q,2H)；2.29(s,3H)；1.12(t,3H)；
examples nos. 1 to 16: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.77(br s,1H)；7.89(d,1H)；7.83(d,1H)；4.01(s,3H)；2.82(t,2H)；2.30(s,3H)；1.66(m,2H)；0.96(t,3H)；
examples nos. 1 to 18: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.67(br s,1H)；7.88(d,1H)；7.83(d,1H)；4.36(q,2H)；2.38(s,3H)；2.35(m,1H)；1.47(t,3H)；1.23(m,4H)；
examples nos. 1 to 21: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.80(br s,1H)；7.92(d,1H)；7.84(d,1H)；4.45(s,2H)；4.01(s,3H)；3.36(s,3H)；2.33(s,3H)；
examples nos. 1-22: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.71(br s,1H)；7.96(d,1H)；7.89(d,1H)；4.97(s,2H)；4.36(q,2H)；2.33(s,3H)；1.47(s,3H)；
examples nos. 1 to 48: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.76(br s,1H)；7.94(d,1H)；7.72(d,1H)；4.01(s,3H)；3.84(s,1H)；2.54(s,3H)；
examples nos. 1-50: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.78(br s,1H)；7.94(d,1H)；7.74(d,1H)；4.01(s,3H)；3.84(s,3H)；2.35(m,1H)；1.16(m,4H)；
examples nos. 1 to 58: 1 H-NMR(400Mhz,CDCl 3 ):δ＝11.06(br s,1H)；7.84(m,2H)；4.16(s,3H)；2.67(s,3H)；2.40(s,3H)；
examples nos. 1 to 60: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.83(br s,1H)；8.03(d,1H)；7.95(d,1H)；4.05(s,3H)；2.37(m,1H)；2.37(s,3H)；1.24(m,4H)；
examples nos. 1 to 65: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.78(br s,1H)；7.85(m,2H)；7.09(t,1H)；4.05(s,3H)；2.61(s,3H)；2.34(s,3H)；
examples nos. 1 to 67: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.78(br s,1H)；7.86(m,2H)；6.97(t,1H)；4.05(3H)；2.36(s,3H)；2.35(m,1H)；1.25(m,2H)；1.20(m,2H)；
examples nos. 1 to 114: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.90(br s,1H)；7.86(d,1H)；7.76(d,1H)；3.99(s,3H)；2.60(s,3H)；
examples nos. 1 to 115: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.90(br s,1H)；7.86(d,1H)；7.76(d,1H)；3.99(s,3H)；2.89(q,2H)；1.14(t,3H)；
examples nos. 1-116: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；7.85(d,1H)；7.76(d,1H)；4.00(s,3H)；2.34(m,1H)；1.23(m,4H)；
examples nos. 1 to 121: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.79(br s,1H)；7.78(d,1H)；7.55(d,1H)；3.98(s,3H)；2.58(s,3H)；2.55(s,3H)；
examples nos. 1 to 123: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.77(br s,1H)；7.76(d,1H)；7.52(d,1H)；3.99(s,3H)；2.57(s,3H)；2.28(m,1H)；1.19(m,4H)；
examples nos. 1-127: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.05(br s,1H)；8.11(m,2H)；4.02(s,3H)；3.29(s,3H)；2.63(s,3H)；
examples nos. 1 to 129: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.04(br s,1H)；8.11(m,2H)；4.02(s,3H)；3.27(s,3H)；2.40(m,1H)；1.26(m,4H)；
examples nos. 1-134: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.76(br s,1H)；7.68(d,1H)；7.43(d,1H)；3.98(s,3H)；2.56(s,3H)；2.28(s,3H)；
examples nos. 1-135: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.78(br s,1H)；7.68(d,1H)；7.42(d,1H)；3.98(s,3H)；2.86(q,2H)；2.25(s,3H)；1.12(t,3H)；
examples nos. 1-136: 1 H-NMR(400Mhz,CDCl 3 ):δ＝10.11(br s,1H)；7.72(d,1H)；7.31(d,1H)；4.10(s,3H)；2.36(s,3H)；2.28(m,1H)；1.38(m,2H)；1.18(m,2H)；
examples nos. 1 to 137: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.00(br s,1H)；8.04(m,2H)；4.02(s,3H)；2.62(s,3H)；
examples nos. 1-138: 1 H-NMR(400Mhz,CDCl 3 ):δ＝11.20(br s,1H)；7.87(d,1H)；7.77(d,1H)；4.13(s,3H)；2.91(q,2H)；1.25(t,3H)；
examples nos. 1-139: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.03(br s,1H)；8.05(m,2H)；4.02(s,3H)；2.98(t,2H)；1.69(m,2H)；0.97(t,3H)；
examples nos. 1-140: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.02(br s,1H)；8.05(m,2H)；4.02(s,3H)；3.08(m,1H)；1.17(d,6H)；
examples nos. 1 to 141: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.02(br s,1H)；8.05(m,2H)；4.02(s,3H)；2.51(s,3H)；2.39(m,1H)；1.25(m,4H)；
examples nos. 1 to 143: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.07(br s,1H)；8.05(s,1H)；4.02(s,3H)；1.26(s,9H)；
examples nos. 1-144: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.06(br s,1H)；8.10(d,1H)；8.05(d,1H)；4.50(s,2H)；3.37(s,3H)；
example nos. 1-145: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.04(br s,1H)；8.14(d,1H)；8.09(d,1H)；4.98(s,2H)；4.02(s,3H)；
example nos. 1-146: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.09(br s,1H)；8.19(d,1H)；8.12(d,1H)；4.01(s,3H)；2.59(s,3H)；
example nos. 1-147: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.05(br s,1H)；8.04(s,2H)；4.02(s,3H)；1.40(d,2H)；1.22(s,3H)；1.13(d,2H)；
example nos. 1-148: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.00(br s,1H)；8.03(m,2H)；4.02(m,3H)；2.07(m,1H)；1.62(m,1H)；1.50(m,1H)；1.18(m,1H)；1.16d,3H)；
example nos. 1-149: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.00(br s,1H)；8.01(m,2H)；4.02(s,3H)；2.22(m,1H)；1.38(m,2H)；1.29(s,3H)；1.22(s,3H)；
examples nos. 1-150: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.07(br s,1H)；8.04(br s,2H)；4.02(s,3H)；1.64(m,2H)；1.17(s,3H)；1.15(s,3H)；0.88(m,1H)；
examples nos. 1 to 153: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.00(br s,1H)；8.02(m,2H)；4.01(s,3H)；3.76(m,1H)；2.32(m,2H)；2.19(m,2H)；1.97(m,1H)；1.83(m,1H)；
examples nos. 1-154: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.01(br s,1H)；8.04(m,2H)；4.02(s,3H)；3.34(m,1H)；1.94(m,2H)；1.79(m,2H)；1.64(m,4H)；
example nos. 1-155: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.01(br s,1H)；8.04(m,2H)；4.02(s,3H)；2.78(m,1H)；1.95(m,2H)；1.78(m,2H)；1.66(m,1H)；1.30(m,4H)；1.17(m,1H)；
examples nos. 1-162: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.13(br s,1H)；8.35(d,1H)；8.27(d,1H)；4.02(s,3H)；
examples nos. 1-163: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.11(br s,1H)；8.25(d,1H)；8.18(d,1H)；7.00(t,1H)；4.02(s,3H)；
examples nos. 1-164: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.95(br s,1H)；7.96(d,1H)；7.81(d,1H)；7.13(t,1H)；4.01(s,3H)；2.60(s.3H)；
example nos. 1-165: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.97(br s,1H)；7.96(d,1H)；7.81(d,1H)；7.11(t,1H)；4.01(s,3H)；2.89(q,2H)；1.13(t,3H)；
examples nos. 1 to 168: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.95(br s,1H)；7.97(d,1H)；7.82(d,1H)；7.05(t,1H)；4.01(s,3H)；2.38(m,1H)；1.23(m,4H)；
example nos. 1-192: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.86(br s,1H)；8.06(d,1H)；7.55(d,1H)；3.99(s,3H)；2.58(s,3H)；
example nos. 1-194: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.87(br s,1H)；8.06(d,1H)；7.54(d,1H)；3.99(s,3H)；2.29(m,1H)；1.25(m,4H)；
examples nos. 1-195: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.00(br s,1H)；8.06(d,1H)；8.02(d,1H)；4.03(s,3H)；2.62(s,3H)；
example nos. 1-197: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.00(br s,1H)；8.05(d,1H)；8.00(d,1H)；8.04(s,3H)；2.36(m,1H)；1.27(m,4H)；
example nos. 1-202: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.94(br s,1H)；7.91(d,1H)；7.84(d,1H)；7.12(t,1H)；4.03(s,3H)；2.6(s,3H)；
example nos. 1-203: 1 H-NMR(400Mhz,CDCl 3 ):δ＝10.77(br s,1H)；7.78(d,1H)；7.75(d,1H)；6.68(t,1H)；4.15(s,3H)；2.95(q,2H)；2.26(t,3H)；
examples nos. 1-204: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.96(br s,1H)；7.92(d,1H)；7.86(d,1H)；7.03(t,1H)；4.03(s,3H)；2.34(m,1H)；1.26(m,4H)；
example nos. 1-231: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.72(br s,1H)；7.84(m,2H)；4.04(s,3H)；2.64(s,3H)；2.28(m,1H)；0.95(m,2H)；5.54(m,2H)；
example nos. 1-233: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.73(br s,1H)；7.83(m,2H)；4.04(s,3H)；2.46(m,1H)；2.25(m,1H)；1.23(m,4H)；0.94(m,2H)；0.57(m,2H)；
examples nos. 1-280: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；7.86(d,1H)；7.76(d,1H)；4.00(s,3H)；3.13(m,1H)；1.19(d,6H)；
example nos. 1-281: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.90(br s,1H)；7.85(d,1H)；7.75(d,1H)；3.99(s,3H)；3.39(q,2H)；1.89(m,4H)；1.65(m,4H)；
example nos. 1-282: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.94(br s,1H)；8.27(d,1H)；7.95(d,1H)；7.83(d,1H)；7.56(m,1H)；7.31(m,1H)；4.00(s,3H)；
example nos. 1-283: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.95(br s,1H)；7.92(d,1H)；7.81(d,2H)；7.76(d,2H)；7.13(d,2H)；4.00(s,3H)；3.88(s,3H)；
example nos. 1-284: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.84(br s,1H)；8.02(d,1H)；7.95(d,1H)；4.05(s,3H)；3.73(m,1H)；2.32(s,3H)；2.32(m,2H)；2.17(m,2H)；1.97(m,1H)；1.82(m,1H)；
example nos. 1-285: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.85(br s,1H)；8.04(d,1H)；7.96(d,1H)；4.05(s,3H)；3.34(m,1H)；2.32(s,3H)；1.92(m,2H)；1.79(m,2H)；1.68(m,2H)；1.58(m,2H)；
examples nos. 1-286: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.85(br s,1H)；8.04(d,1H)；
7.96(d,1H)；4.05(s,3H)；2.77(m,1H)；2.30(s,3H)；1.94(m,2H)；1.77(m,2H)；1.65(m,1H)；1.29(m,4H)；1.14(m,1H)；
example nos. 1-287: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.01(br s,1H)；8.15(m,2H)；7.76(m,1H)；7.54(m,2H)；4.01(s,3H)；
examples nos. 1-289: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.89(br s,1H)；7.89(d,1H)；7.77(d,1H)；3.99(s,3H)；2.59(s,3H)；
example nos. 1-291: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.89(br s,1H)；7.89(d,1H)；7.76(d,1H)；4.00(s,3H)；2.32(m,1H)；1.24(m,4H)；
example nos. 1-292: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.67(br s,1H)；7.72(d,1H)；7.57(d,1H)；3.89(s,3H)；2.57(s,3H)；2.29(s,3H)；
example nos. 1-293: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.64(br s,1H)；7.71(d,1H)；7.56(d,1H)；3.98(s,3H)；2.86(q,2H)；2.26(s,3H)；1.12(t,3H)；
example nos. 1-294: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.65(br s,1H)；7.70(d,1H)；7.56(d,1H)；3.97(s,3H)；2.30(s,3H)；2.29(m,1H)；1.17(m,4H)；
example No. 2-1: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.38(br s,1H)；7.56(d,1H)；7.25(d,1H)；4.32(q,2H)；2.50(s,3H)；2.27(s,3H)；2.24(s,3H)；1.46(t,3H)；
examples nos. 2 to 7: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.70(br s,1H)；7.97(d,1H)；7.92(d,1H)；4.36(q,2H)；3.22(s,3H)；2.59(s,3H)；2.35(s,3H)；1.47(t,3H)；
examples nos. 2 to 9: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.72(br s,1H)；7.98(d,1H)；7.92(d,1H)；4.36(q,2H)；3.21(s,3H)；2.41(s,3H)；2.38(m,1H)；1.48(t,3H)；1.23(m,4H)；
examples nos. 2 to 14: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.67(br s,1H)；7.88(d,1H)；7.83(d,1H)；4.36(q,2H)；2.57(s,3H)；2.34(s,3H)；1.47(t,3H)；
examples nos. 2 to 15: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.67(br s,1H)；7.88(d,1H)；7.83(d,1H)；4.34(q,2H)；2.85(q,2H)；2.29(s,3H)；1.47(t,3H)；1.12(t,3H)；
examples nos. 2 to 16: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.67(br s,1H)；7.88(d,1H)；7.83(d,1H)；4.35(q,2H)；2.83(t,2H)；2.30(s,3H)；1.67(m,2H)；1.47(t,3H)；0.96(t,3H)；
examples nos. 2 to 18: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.68(br s,1H)；7.88(d,1H)；7.84(d,1H)；4.36(q,2H)；2.38(s,3H)；2.35(m,1H)；1.48(t,3H)；1.23(m,4H)；
examples nos. 2 to 22: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.83(br s,1H)；7.97(d,1H)；7.89(d,1H)；4.97(s,3H)；2.33(s,3H)；
examples nos. 2 to 48: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.65(br s,1H)；7.93(d,1H)；7.72(d,1H)；4.35(q,2H)；3.84(s,3H)；2.55(s,3H)；1.47(t,3H)；
examples nos. 2 to 50: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.63(br s,1H)；7.94(d,1H)；7.74(d,1H)；4.35(q,2H)；3.84(s,3H)；2.37(m,1H)；1.48(t,3H)；1.18(m,4H)；
example nos. 2-58: 1 H-NMR(400Mhz,CDCl 3 ):δ＝10.85(br s,1H)；7.88(d,1H)；7.83(d,1H)；4.52(q,2H)；2.67(s,3H)；2.41(s,3H)；1.64(t,3H)；
examples nos. 2 to 60: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.74(br s,1H)；8.03(d,1H)；7.94(d,1H)；4.43(q,2H)；2.37(s,3H)；2.36(m,1H)；1.49(t,3H)；1.24(m,4H)；
example nos. 2-65: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.68(br s,1H)；7.84(m,2H)；7.09(t,1H)；4.42(q,2H)；2.62(s,3H)；2.35(s,3H)；1.49(t,3H)；
examples nos. 2 to 67: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.68(br s,1H)；7.86(s,2H)；6.97(t,1H)；4.43(q,2H)；2.36(s,3H)；2.36(m,1H)；1.49(t,3H)；1.26(m,2H)；1.20(m,2H)；
example nos. 2-114: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.80(br s,1H)；7.85(d,1H)；7.76(d,1H)；4.35(q,2H)；3.99；2.60(s,3H)；1.46(t,3H)；
example nos. 2-115: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.80(br s,1H)；7.86(d,1H)；7.76(d,1H)；4.35(q,2H)；2.89(q,2H)；1.46(t,3H)；1.14(t,3H)；
example nos. 2-116: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.81(br s,1H)；7.85(d,1H)；7.76(d,1H)；4.36(q,2H)；2.34(m,1H)；1.47(t,3H)；1.23(m,4H)；
example nos. 2-121: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.69(br s,1H)；7.76(d,1H)；7.55(d,1H)；4.34(q,2H)；2.58(s,3H)；2.55(s,3H)；1.46(t,3H)；
example nos. 2-123: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.68(br s,1H)；7.75(d,1H)；7.52(d,1H)；4.35(q,2H)；2.57(s,3H)；2.28(m,1H)；1.46(t,3H)；1.20(m,4H)；
example numbering2-127: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.95(br s,1H)；8.12(m,2H)；4.35(q,2H)；3.29(s,3H)；2.64(s,3H)；1.47(t,3H)；
Example nos. 2 to 129: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.95(br s,1H)；8.11(m,2H)；4.38(q,2H)；3.27(s,3H)；2.40(m,1H)；1.48(t,3H)；1.26(m,4H)；
examples nos. 2 to 134: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.66(br s,1H)；7.67(d,1H)；7.43(d,1H)；4.35(q,2H)；2.56(s,3H)；2.28(s,3H)；1.46(t,3H)；
example nos. 2-135: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.66(br s,1H)；7.67(d,1H)；7.43(d,1H)；4.34(q,2H)；2.86(q,2H)；2.25(s,3H)；1.46(t,3H)；1.12(t,3H)；
examples nos. 2 to 136: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.67(br s,1H)；7.68(d,1H)；7.44(d,1H)；4.35(q,2H)；2.32(m,1H)；2.31(s,3H)；1.46(t,3H)；1.18(m,4H)；
example nos. 2-137: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.05(d,1H)；8.02(d,1H)；4.37(q,2H)；2.62(s,3H)；1.47(t,3H)；
example nos. 2 to 139: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.93(br s,1H)；8.03(m,2H)；4.36(q,2H)；2.89(m,2H)；1.68(m,2H)；1.47(t,3H)；0.97(t,3H)；
example nos. 2-140: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.93(br s,1H)；8.03(m,2H)；4.37(q,2H)；3.07(m,1H)；1.47(t,3H)；1.17(d,6H)；
example nos. 2-141: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.03(m,2H)；4.38(q,2H)；2.39(m,1H)；1.47(t,3H)；1.25(m,4H)；
example nos. 2 to 143: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.97(br s,1H)；8.05(s,2H)；4.37(q,2H)；1.47(t,3H)；1.25(s,9H)；
example nos. 2-144: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.96(br s,1H)；8.09(d,1H)；8.04(d,1H)；4.50(s,2H)；4.37(q,2H)；3.37(s,3H)；1.47(t,3H)；
example nos. 2-145: 1 H-NMR(400Mhz,CDCl 3 ):δ＝11.15(br s,1H)；7.95(d,1H)；7.81(d,1H)；4.64(s,2H)；4.51(q,2H)；1.63(t,3H)；
example nos. 2-147: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.95(br s,1H)；8.04(s,2H)；4.38(q,2H)；1.48(t,3H)；1.40(d,2H)；1.22(s,3H)；1.13(d,2H)；
example nos. 2-148: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.90(br s,1H)；8.02(m,2H)；4.38(q,2H)；2.14(m,1H)；1.64(m,1H)；1.49(m,1H)；1.48(t,3H)；1.16(m,1H)；1.16(d,3H)；
example nos. 2-149: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.01(m,2H)；4.37(q,2H)；2.22(m,1H)；1.48(t,3H)；1.35(m,2H)；1.29(s,3H)；1.22(s,3H)；
example nos. 2-150: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.99(br s,1H)；8.03(br s,2H)；4.38(q,2H)；1.63(m,2H)；1.48(t,3H)；1.17(s,3H)；1.15(s,3H)；0.88(m,1H)；
example nos. 2-153: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.02(m,2H)；4.37(q,2H)；3.75(m,1H)；2.31(m,2H)；2.20(m,2H)；1.99(m,1H)；1.83(m,1H)；1.47(t,3H)；
example nos. 2-154: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.92(br s,1H)；8.04(m,2H)；4.37(q,2H)；3.34(m,1H)；1.94(m,2H)；1.79(m,2H)；1.63(m,4H)；1.48(t,3H)；
example nos. 2-155: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.93(br s,1H)；8.04(d,1H)；8.01(d,1H)；4.36(q,2H)；2.77(m,1H)；1.95(m,2H)；1.78(m,2H)；1.65(m,1H)；1.47(t,3H)；1.30(m,4H)；1.15(m,1H)；
example nos. 2-162: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.03(br s,1H)；8.34(d,1H)；8.27(d,1H)；4.38(q,2H)；1.48(t,3H)；
example No. 2-163: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝12.00(br s,1H)；8.24(d,1H)；8.17(d,1H)；7.00(t,1H)；4.37(q,2H)；1.48(t,3H)；
Example nos. 2-164: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.85(br s,1H)；7.96(d,1H)；7.81(d,1H)；7.14(t,1H)；4.37(q,2H)；2.60(3H)；1.47(t,3H)；
example nos. 2-165: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.88(br s,1H)；7.96(d,1H)；7.81(d,1H)；7.11(t,1H)；4.37(q,2H)；2.90(q,2H)；1.47(t,3H)；1.13(t,1H)；
example nos. 2-168: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.86(br s,1H)；7.97(d,1H)；7.82(d,1H)；7.05(t,1H)；4.37(q,2H)；2.38(m,1H)；1.47(t,3H)；1.24(m,4H)；
example nos. 2-194: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.78(br s,1H)；8.06(d,1H)；7.53(d,1H)；4.35(q,2H)；2.29(m,1H)；1.46(t,3H)；1.25(m,4H)；
example nos. 2-195: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.89(br s,1H)；8.05(d,1H)；7.99(d,1)；4.39(q,2H)；2.62(s,3H)；1.48(t,3H)；
example nos. 2-197: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.07(d,1H)；8.00(d,1H)；4.41(q,2H)；2.38(m,1H)；1.50(t,3H)；1.29(m,4H)；
example nos. 2-202: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.83(br s,1H)；7.91(d,1H)；7.84(d,1H)；7.12(t,1H)；4.39(q,2H)；2.60(s,3H)；1.48(t,3H)；
example nos. 2-204: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.86(br s,1H)；7.91(d,1H)；7.86(d,1H)；7.03(t,1H)；4.39(q,2H)；2.37(m,1H)；1.48(t,3H)；1.25(m,4H)；
example nos. 2-231: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.60(br s,1H)；7.84(m,2H)；4.38(q,2H)；2.64(s,3H)；2.28(m,1H)；1.50(t,3H)；0.94(m,2H)；0.55(m,2H)；
example nos. 2-233: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.60(br s,1H)；7.84(m,2H)；4.38(q,2H)；2.44(m,1H)；2.23(m,1H)；1.50(t,3H)；1.22(m,4H)；0.94(m,2H)；0.57(m,2H)；
example nos. 2-280: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.81(br s,1H)；7.86(d,1H)；7.76(d,1H)；4.35(q,2H)；3.13(m,1H)；1.47(t,3H)；1.19(d,6H)；
example nos. 2-281: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.80(br s,1H)；7.85(d,1H)；7.75(d,1H)；4.35(q,2H)；3.39(m,1H)；1.88(m,4H)；1.64(m,4H)；1.46(t,3H)；
example nos. 2-282: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.85(br s,1H)；8.27(d,1H)；7.95(d,1H)；7.83(d,1H)；7.57(m,1H)；7.31(m,1H)；4.36(q,2H)；1.46(t,3H)；
example nos. 2-283: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.84(br s,1H)；7.92(d,1H)；7.81(d,1H)；7.76(d,2H)；7.13(d,2H)；4.35(q,2H)；3.88(s,3H)；1.46(t,3H)；
example nos. 2-284: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.73(br s,1H)；8.02(d,1H)；7.93(d,1H)；4.42(q,2H)；3.73(m,1H)；2.33(s,3H)；2.32(m,2H)；2.18(m,2H)；1.97(m,1H)；1.82(m,1H)；1.48(t,3H)；
example nos. 2-285: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.77(br s,1H)；8.04(d,1H)；7.95(d,1H)；4.44(q,2H)；2.78(m,1H)；2.32(s,3H)；1.95(m,2H)；1.79(m,2H)；1.65(m,1H)；1.50(t,3H)；1.28(m,4H)；1.16(m,1H)；
example nos. 2-286: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.93(br s,1H)；8.15(m,2H)；7.76(m,1H)；7.54(m,2H)；4.36(q,2H)；1.46(t,3H)；
example nos. 2-288: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.79(br s,1H)；7.89(d,1H)；7.76(d,1H)；4.35(q,2H)；2.59(s,3H)；1.46(t,3H)；
examples nos. 2 to 290: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.80(br s,1H)；7.89(d,1H)；7.75(d,1H)；4.35(q,2H)；2.32(m,1H)；1.46(t,3H)；1.24(m,4H)；
example nos. 2-291: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.57(br s,1H)；7.71(d,1H)；7.57(d,1H)；4.33(q,2H)；2.57(s,3H)；2.29(s,3H)；1.46(t,3H)；
example nos. 2-292: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.53(br s,1H)；7.71(d,1H)；7.56(d,1H)；4.33(q,2H)；2.86(q,2H)；2.26(s,3H)；1.46(t,3H)；1.12(t,3H)；
example nos. 2-293: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.54(br s,1H)；7.71(d,1H)；7.57(d,1H)；4.33(q,2H)；2.31(s,3H)；2.31(m,1H)；1.46(t,3H)；1.19(m,4H)；
example nos. 2-294: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.92(br s,1H)；8.07(m,2H)；6.74(dd,1H)；6.45(d,1H)；6.00(d,1H)；4.37(q,2H)；1.47(t,3H)；
example No. 3-1: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.36(br s,1H)；7.55(d,1H)；7.26(d,1H)；4.27(t,2H)；2.51(s,3H)；2.26(s,3H)；2.24(s,3H)；1.88(m,2H)；0.87(t,3H)；
example nos. 3 to 3: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.37(br s,1H)；7.56(d,1H)；7.28(d,1H)；4.28(t,2H)；2.30(s,3H)；2.28(m,1H)；2.27(s,3H)；1.16(m,4H)；0.87(t,3H)；
examples nos. 3 to 7: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.68(br s,1H)；7.97(d,1H)；7.91(d,1H)；4.30(t,2H)；3.22(s,3H)；2.59(s,3H)；2.35(s,3H)；1.89(m,2H)；0.89(t,3H)；
examples nos. 3 to 9: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.70(br s,1H)；7.98(d,1H)；7.91(d,1H)；4.31(t,2H)；3.21(s,3H)；2.41(s,3H)；2.36(m,1H)；1.89(m,2H)；1.23(m,4H)；0.89(t,3H)；
examples nos. 3 to 14: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.64(br s,1H)；7.86(d,1H)；7.83(d,1H)；4.30(t,2H)；2.57(s,3H)；2.33(s,3H)；1.89(m,2H)；0.89(t,3H)；
examples nos. 3 to 15: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.64(br s,1H)；7.87(d,1H)；7.83(d,1H)；4.30(t,2H)；2.85(q,2H)；2.29(s,3H)；1.89(m,2H)；1.12(t,3H)；0.89(s,3H)；
examples nos. 3 to 16: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.65(br s,1H)；7.86(d,1H)；7.83(d,1H)；4.30(t,2H)；2.83(t,2H)；2.30(s,3H)；1.89(m,2H)；1.66(m,2H)；0.96(t,3H)；0.89(t,3H)；
examples nos. 3 to 18: 1 H-NMR(400Mhz,CDCl 3 ):δ＝11.00(br s,1H)；7.85(d,1H)；7.68(d,1H)；4.39(q,2H)；2.49(s,3H)；2.25(m,1H)；2.01(m,2H)；1.42(m,2H)；1.21(m,2H)；0.98(t,3H)；
example nos. 3 to 48: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.66(br s,1H)；7.92(d,1H)；7.72(d,1H)；4.30(t,2H)；3.84(s,3H)；2.55(s,3H)；1.89(m,2H)；0.89(t,3H)；
examples nos. 3 to 50: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.60(br s,1H)；7.93(d,1H)；7.74(d,1H)；4.30(t,2H)；3.84(s,3H)；2.37(m,1H)；1.89(m,2H)；1.18(m,4H)；0.89(t,3H)；
example nos. 3-58: 1 H-NMR(400Mhz,CDCl 3 ):δ＝10.83(br s,1H)；7.86(d,1H)；7.82(d,1H)；4.45(t,2H)；2.67(s,3H)；2.40(s,3H)；2.05(m,2H)；1.00(t,3H)；
example nos. 3-65: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.68(br s,1H)；7.84(s,2H)；7.09(t,1H)；4.37(t,2H)；2.62(3H)；2.35(s,3H)；1.91(2H)；0.90(t,3H)；
example nos. 3 to 67: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.68(br s,1H)；7.85(s,2H)；6.97(t,1H)；4.37(t,2H)；2.38(m,1H)；2.36(s,3H)；1.91(m,2H)；1.23(m,4H)；0.90(t,3H)；
example nos. 3-123: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.66(br.s,1H)；7.74(d,1H)；7.52(d,1H)；4.30(t,2H)；2.57(s,3H)；2.28(m,1H)；1.88(m,2H)；1.19(m,4H)；0.87(t,3H)；
example nos. 3 to 129: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.93(br s,1H)；8.12(d,1H)；8.08(d,1H)；4.32(t,2H)；3.27(s,3H)；2.40(m,1H)；1.89(m,2H)；1.26(m,4H)；0.88(t,3H)；
example nos. 3-134: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.65(br s,1H)；7.66(d,1H)；7.43(d,1H)；4.30(t,2H)；2.56(s,3H)；2.28(s,3H)；1.88(m,2H)；0.87(t,3H)；
example nos. 3-135: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.65(br s,1H)；7.66(d,1H)；7.43(d,1H)；4.29(t,2H)；2.86(q,2H)；2.25(s,3H)；1.88(m,2H)；1.12(t,3H)；0.87(t,3H)；
example nos. 3-136: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.65(br s,1H)；7.66(d,1H)；7.44(d,1H)；4.30(t,2H)；2.32(m,1H)；2.30(s,3H)；1.88(m,2H)；1.19(m,4H)；0.87(t,3H)；
example nos. 3-137: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.89(br s,1H)；8.02(m,2H)；4.32(t,2H)；2.62(s,3H)；1.89(m,2H)；0.88(t,3H)；
example nos. 3-140: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.04(s,2H)；4.32(t,2H)；3.07(m,1H)；1.89(m,2H)；1.17(d,6H)；0.88(t,3H)；
example nos. 3 to 141: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.89(br s,1H)；8.03(m,2H)；4.32(t,2H)；2.40(m,1H)；1.89(m,2H)；1.25(m,4H)；0.88(t,3H)；
example nos. 3-144: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.94(br s,1H)；8.05(m,2H)；4.50(s,2H)；4.32(t,2H)；3.37(s,3H)；1.88(m,2H)；0.88(t,3H)；
examples nos. 3 to 150: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.93(br s,1H)；8.02(br s,2H)；4.33(t,2H)；1.91.89(m,2H)；1.63(m,2H)；1.17(s,3H)；1.15(s,3H)；0.88(t,3H)；0.87(m,1H)；
example nos. 3-153: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.03(m,2H)；4.33(t,2H)；3.77(m,1H)；2.34(m,2H)；2.21(m,2H)；2.01(m,1H)；1.88(m,3H)；0.90(t,3H)；
example nos. 3 to 155: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.90(br s,1H)；8.03(br s,2H)；4.32(t,2H)；2.77(m,1H)；1.94(m,4H)；1.99(m,2H)；1.78(m,2H)；1.65(m,1H)；1.29(m,2H)；1.15(m,1H)；0.88(t,3H)；
example nos. 3-163: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.98(br s,1H)；8.23(d,1H)；8.17(d,1H)；7.01(t,1H)；4.32(t,2H)；1.89(m,2H)；0.89(t,3H)；
example nos. 3-164: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.83(br s,1H)；7.95(d,1H)；7.81(d,1H)；7.14(t,1H)；4.32(t,2H)；2.60(s,3H)；1.89(m,2H)；0.88(t,3H)；
example nos. 3-165: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.86(br s,1H)；7.95(d,1H)；7.81(d,1H)；7.11(t,1H)；4.31(t,2H)；2.90(q,2H)；1.89(m,2H)；1.13(t,3H)；0.88(t,3H)；
example nos. 3-168: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.84(br s,1H)；7.95(d,1H)；7.83(d,1H)；7.05(t,1H)；4.32(t,2H)；2.38(m,1H)；1.89(m,2H)；1.24(m,4H)；0.88(t,3H)；
example nos. 3-192: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.75(br s,1H)；8.06(d,1H)；7.53(d,1H)；4.29(t,2H)；2.58(s,3H)；1.87(m,2H)；0.87(t,3H)；
example nos. 3-195: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.87(br s,1H)；8.05(d,1H)；7.98(d,1H)；4.34(t,2H)；2.62(s,3H)；1.90(m,2H)；0.89(t,3H)；
example nos. 3-197: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.89(br s,1H)；8.07(d,1H)；7.99(d,1H)；4.35(t,2H)；2.38(m,1H)；1.93(m,2H)；1.29(m,4H)；0.91(t,3H)；
example nos. 3-202: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.82(br s,1H)；7.89(d,1H)；7.84(d,1H)；4.33(t,2H)；2.60(s,3H)；1.90(m,2H)；0.89(t,3H)；
example nos. 3-204: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.81(br s,1H)；7.89(d,1H)；7.85(d,1H)；7.02(t,1H)；4.33(t,2H)；2.36(m,1H)；1.89(m,2H)；1.26(m,4H)；0.89(t,3H)；
example nos. 3-231: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.58(br s,1H)；7.85(d,1H)；7.80(d,1H)；4.33(t,2H)；2.64(s,3H)；2.27(m,1H)；1.91(m,2H)；0.94(m,2H)；0.90(t,3H)；0.55(m,2H)；
example nos. 3-280: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.73(br s,1H)；8.02(d,1H)；7.92(d,1H)；4.36(t,2H)；3.74(m,1H)；2.33(s,3H)；2.33(m,2H)；2.18(m,2H)；1.94(m,3H)；1.83(m,1H)；0.89(t,3H)；
example nos. 3-281: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.74(br s,1H)；8.04(d,1H)；7.94(d,1H)；4.37(t,2H)；2.77(m,1H)；2.32(s,3H)；1.94(m,2H)；1.92(m,2H)；1.77(m,2H)；1.65(m,1H)；1.26(m,4H)；1.14(m,1H)；0.90(s,3H)；
example nos. 3-282: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.91(br s,1H)；8.15(m,2H)；7.77(m,1H)；7.54(m,2H)；4.31(t,2H)；1.88(m,2H)；0.87(t,3H).
example nos. 3-284: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.78(br s,1H)；7.89(d,1H)；7.75(d,1H)；4.30(t,2H)；2.59(s,3H)；1.88(m,2H)；0.87(t,3H)；
example nos. 3-286: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.78(br s,1H)；7.89(d,1H)；7.74(d,1H)；4.30(t,2H)；2.32(m,1H)；1.88(m,2H)；1.24(m,4H)；0.87(t,3H)；
example nos. 3-287: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.54(br s,1H)；7.70(d,1H)；7.57(d,1H)；4.28(t,2H)；2.57(s,3H)；2.29(s,3H)；1.87(m,2H)；0.88(t,3H)；
example nos. 3-288: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.51(br s,1H)；7.69(d,1H)；7.56(d,1H)；4.28(t,2H)；2.86(q,2H)；2.26(s,3H)；1.88(m,2H)；1.12(t,3H)；0.88(t,3H)；
examples nos. 3-289: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝11.52(br s,1H)；7.69(d,1H)；7.58(d,1H)；4.29(t,2H)；2.31(s,3H)；2.31(m,1H)；1.88(m,2H)；2.20(m,4H)；0.88(t,3H)；
example No. 4-2: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.95(d,1H)；7.77(d,1H)；3.89(s,3H)；2.83(q,2H)；2.34(s,3H)；1.10(t,3H)；
example nos. 4 to 3: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.94(d,1H)；7.77(d,1H)；3.89(s,3H)；2.80(t,2H)；2.34(s,3H)；1.65(m,2H)；0.95(t,3H)；
example nos. 4 to 5: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.95(d,1H)；7.78(d,1H)；3.89(s,3H)；3.32(s,3H)；2.42(s,3H)；2.35(m,1H)；1.21(m,4H)；
example nos. 4 to 8: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.97(d,1H)；7.79(d,1H)；4.43(s,2H)；3.89(s,3H)；3.34(s,3H)；2.37(s,3H)；
example nos. 4 to 9: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.01(d,1H)；7.83(d,1H)；4.95(s,3H)；3.90(s,3H)；2.37(s,3H)；
example nos. 4 to 35: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.98(d,1H)；7.67(d,1H)；3.92(s,3H)；3.78(s,3H)；2.51(s,3H)；
example nos. 4-37: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.98(d,1H)；7.68(d,1H)；3.92(s,3H)；3.78(s,3H)；2.35(m,1H)；1.15(m,4H)；
example nos. 4 to 45: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.97(d,1H)；7.87(d,1H)；3.92(s,3H)；2.60(s,3H)；2.33(s,3H)；
examples nos. 4 to 49: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.97(m,1H)；7.86(d,1H)；3.92(s,3H)；2.38(m,1H)；2.34(s,3H)；1.21(m,4H)；
example nos. 4 to 61: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.95(d,1H)；7.86(d,1H)；3.91(s,3H)；3.71(m,1H)；2.31(m,2H)；2.31(s,3H)；2.16(m,2H)；1.94(m,1H)；1.80(m,1H)；
example nos. 4-62: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.97(d,1H)；7.86(d,1H)；3.91(s,3H)；3.31(m,1H)；2.29(s,3H)；1.90(m,2H)；1.75(m,2H)；1.66(m,2H)；1.56(m,2H)；
example nos. 4 to 63: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.98(d,1H)；7.86(d,1H)；3.91(s,3H)；2.73(m,1H)；2.28(s,3H)；1.91(m,2H)；1.75(m,2H)；1.63(m,1H)；1.24(m,4H)；1.11(m,1H)；
example nos. 4 to 74: 1 H-NMR(400Mhz,CDCl 3 ):δ＝7.69(br s,2H)；6.64(t,1H)；3.97(s,3H)；2.37(s,3H)；2.32(m,1H)；1.42(m,2H)；1.18(m,2H)；
examples nos. 4 to 99: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.04(d,1H)；7.77(d,1H)；3.92(s,3H)；3.60(s,3H)；
example nos. 4-100: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.05(d,1H)；7.97(d,1H)；3.92(s,3H)；2.89(q,2H)；1.12(t,3H)；
example nos. 4 to 101: 1 H-NMR(400Mhz,CDCl 3 ):δ＝7.87(d,1H)；7.65(d,1H)；3.97(s,3H)；2.83(t,2H)；1.68(m,2H)；1.02(t,3H)；
example nos. 4-102: 1 H-NMR(400Mhz,CDCl 3 ):δ＝7.86(d,1H)；7.66(d,1H)；3.97(s,1H)；3.05(m,1H)；1.24(d,6H)；
example nos. 4 to 103: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.04(d,1H)；7.97(d,1H)；3.92(s,3H)；2.41(m,1H)；1.23(m,4H)；
example nos. 4 to 105: 1 H-NMR(400Mhz,CDCl 3 ):δ＝7.83(d,1H)；7.66(d,1H)；3.97(s,3H)；1.30(s,9H)；
example nos. 4-106: 1 H-NMR(400Mhz,CDCl 3 ):δ＝7.93(d,1H)；7.67(d,1H)；4.42(s,2H)；3.98(s,3H)；3.47(s,3H)；
example nos. 4 to 107: 1 H-NMR(400Mhz,CDCl 3 ):δ＝7.98(d,1H)；7.71(d,1H)；4.54(s,2H)；3.99(s,3H)；
example nos. 4-108: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.19(d,1H)；8.06(d,1H)；3.92(s,3H)；2.58(s,3H)；
example nos. 4 to 109: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.05(d,1H)；7.99(d,1H)；3.92(s,3H)；1.39(m,2H)；1.18(s,3H)；1.12(m,2H)；
example nos. 4 to 110: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.03(d,1H)；7.96(d,1H)；3.92(s,3H)；2.18(m,1H)；1.511(m,1H)；1.49(m,1H)；1.14(d,3H)；1.14(m,1H)；
example nos. 4 to 111: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.01(d,1H)；7.94(d,1H)；3.92(s,3H)；2.26(m,1H)；1.31(m,2H)；1.28(s,3H)；1.20(s,3H)；
example nos. 4-112: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.04(d,2H)；7.98(2xd,2H)；3.92(6H)；1.63(m,4H)；1.15(m,7H)；0.86(m,1H)；
example nos. 4 to 115: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.03(d,1H)；7.96(d,1H)；3.92(s,3H)；3.75(m,1H)；2.31(m,2H)；1.17(m,2H)；1.97(m,1H)；1.81(m,1H)；
example nos. 4-116: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.04(d,1H)；7.97(d,1H)；3.92(s,3H)；3.32(m,1H)；1.92(m,2H)；1.76(m,2H)；1.62(m,4H)；
example nos. 4-117: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.04(d,1H)；7.98(d,1H)；3.92(s,3H)；2.75(m,1H)；1.92(m,2H)；1.76(m,2H)；1.63(m,1H)；1.29(m,4H)；1.15(m,1H)；
example nos. 4-124: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.09(d,1H)；7.75(d,1H)；4.00(s,3H)；
example nos. 4-125: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.24(d,1H)；8.12(d,1H)；6.99(t,1H)；3.95(s,3H)；
example nos. 4-126: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.98(d,1H)；7.77(d,1H)；7.11(t,1H)；3.91(s,3H)；2.58(s,3H)；
example nos. 4-127: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.98(d,1H)；7.76(d,1H)；7.08(t,1H)；3.90(s,3H)；2.87(q,2H)；1.11(t,3H)；
example nos. 4-130: 1 H-NMR(400Mhz,CDCl 3 ):δ＝7.88(d,1H)；7.64(d,1H)；6.68(t,1H)；3.97(s,3H)；2.33(m,1H)；1.42(m,2H)；1.20(m,2H)；
example nos. 4-153: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.00(d,1H)；7.96(d,1H)；3.92(s,3H)；2.60(s,3H)；
example nos. 4-155: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.00(d,1H)；7.95(d,1H)；3.92(s,3H)；2.39(m,1H)；1.25(m,4H)；
example nos. 4-160: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.90(d,1H)；7.80(d,1H)；7.09(t,1H)；3.91(s,3H)；2.58(s,3H)；
example nos. 4-161: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.90(d,1H)；7.80(d,1H)；7.06(t,1H)；3.90(s,6H)；2.87(q,2H)；1.13(t,3H)；
example nos. 4-162: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.90(d,1H)；7.81(d,1H)；3.91(s,3H)；2.37(m,1H)；1.23(m,4H)；
example nos. 4-187: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.79(d,1h)；7.76(d,1H)；3.90(s,3H)；2.63(s,3H)；2.21(m,1H)；0.92(m,2H)；0.38(m,1H)；
example nos. 4-189: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝7.79(d,1H)；7.75(d,1H)；3.90(s,3H)；2.46(m,1H)；2.15(m,1H)；1.20(m,4H)；0.92(m,2H)；0.41(m,2H)；
example nos. 4 to 201: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.19(d,1H)；8.08(d,1H)；7.73(m,1H)；7.58(m,2H)；3.92(s,3H)；
example nos. 4 to 203: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.09(d,1H)；8.01(d,1H)；6.72(dd,1H)；6.39(d,1H)；6.00(d,1H)；3.92(s,3H)；
example nos. 4 to 204: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.08(d,1H)；7.99(d,1H)；6.27(s,1H)；5.59(s,1H)；3.92(s,3H)；1.97(s,3)；
example nos. 4-205: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.06(m,2H)；7.97(m,2H)；6.61(2xd,2H)；6.48(2xd,2H)；3.92(2xs,6H)；2.03(d,3H)；1.93(d,3H)；
example nos. 4 to 206: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.01(4xd,4H)；6.53(br q,1H)；6.35(q,1H)；3.92(s,3H)；3.91(s,3H)；1.86(m,6H)；
example nos. 4 to 207: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.01(d,1H)；7.94(d,1H)；6.35(br s,1H)；3.91(s,3H)；2.14(s,3H)；1.98(s,3H)；
example nos. 4 to 213: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.14(d,1H)；8.04(d,1H)；5.54(s,1H)；3.93(s,3H)；
example nos. 4-214: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝8.09(d,1H)；8.01(d,1H)；3.93(s,3H)；2.18(s,3H)；
example No. 5-2: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.61(br s,1H)；7.93(d,1H)；7.74(d,1H)；2.82(q,2H)；2.34(s,3H)；1.10(t,3H)；
example nos. 5 to 3: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.60(br s,1H)；7.92(d,1H)；7.74(d,1H)；2.80(t,2H)；2.36(s,3H)；1.64(m,2H)；0.95(t,3H)；
example nos. 5 to 5: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.59(br s,1H)；7.93(d,1H)；7.75(d,1H)；2.37(s,3H)；2.34(m,1H)；1.20(m,4H)；
examples nos. 5 to 8: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.61(br s,1H)；7.95(d,1H)；7.74(d,1H)；4.42(s,2H)；3.34(s,3H)；2.38(s,3H)；
example nos. 5 to 9: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.68(br s,1H)；8.00(d,1H)；7.79(d,1H)；4.94(s,3H)；2.39(s,3H)；
example nos. 5 to 35: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.71(br s,1H)；7.94(d,1H)；7.62(d,1H)；3.79(s,3H)；2.50(s,3H)；
example nos. 5-37: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.69(br s,1H)；7.95(d,1H)；7.64(d,1H)；3.79(s,3H)；2.34(m,1H)；1.15(m,4H)；
example nos. 5 to 45: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.84(br s,1H)；7.92(d,1H)；7.81(d,1H)；2.59(s,3H)；2.34(s,3H)；
example nos. 5-49: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.80(br s,1H)；7.92(d,1H)；7.80(d,1H)；2.39(m,1H)；2.38(s,3H)；1.21(m,4H)；
example nos. 5 to 61: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.82(br s,1H)；7.90(d,1H)；7.80(d,1H)；3.71(m,1H)；2.33(s,3H)；2.29(m,2H)；2.15(m,2H)；1.94(m,1H)；1.80(m,1H)；
example nos. 5 to 62: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.83(br s,1H)；7.92(d,1H)；8.00(d,1H)；3.32(m,1H)；2.31(s,3H)；1.90(m,2H)；1.76(m,2H)；1.64(m,2H)；1.57(m,2H)；
example nos. 5 to 63: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.83(br s,1H)；7.92(d,1H)；7.80(d,1H)；2.71(m,1H)；2.31(s,3H)；1.91(m,2H)；1.75(m,2H)；1.64(m,1H)；1.25(m,4H)；1.11(m,1H)；
example nos. 5-72: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.00(d,1H)；7.72(d,1H)；6.70(t,1H)；2.67(s,3H)；2.42(s,3H)；
example nos. 5-74: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.06(d,1H)；7.77(d,1H)；6.66(t,1H)；2.43(s,3H)；2.31(m,1H)；1.44(m,2H)；1.22(m,2H)；
examples nos. 5 to 99: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.07(d,1H)；7.71(d,1H)；2.63(s,3H)；
example nos. 5-100: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.98(br s,1H)；7.99(d,1H)；7.92(d,1H)；2.88(q,2H)；1.11(t,3H)；
example nos. 5 to 101: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.05(d,1H)；7.70(d,1H)；2.85(t,2H)；1.82(m,2H)；1.03(t,3H)；
example nos. 5-102: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.06(d,1H)；7.71(d,1H)；3.06(m,1H)；1.25(d,6H)；
example nos. 5 to 103: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.11(br s,1H)；8.00(d,1H)；7.92(d,1H)；2.38(m,1H)；1.19(m,4H)；
example nos. 5 to 105: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.02(d,1H)；7.71(d,1H)；1.32(s,9H)；
example nos. 5-106: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.11(d,1H)；7.72(d,1H)；4.43(s,2H)；3.48(s,3H)；
example nos. 5 to 107: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.14(d,1H)；7.75(d,1H)；4.54(s,2H)；
example nos. 5-108: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.21(br s,1H)；8.14(d,1H)；8.02(d,1H)；2.58(s,3H)；
examples nos. 5 to 109: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.11(br s,1H)；7.99(d,1H)；7.94(d,1H)；1.38(m,2H)；1.19(s,3H)；1.11(m,2H)；
examples nos. 5 to 110: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.07(br s,1H)；7.97(d,1H)；7.91(d,1H)；2.15(m,1H)；1.60(m,1H)；1.48(m,1H)；1.15(d,3H)；1.11(m,1H)；
examples Nos. 5 to 111: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.01(br s,1H)；7.97(d,1H)；7.90(d,1H)；2.24(m,1H)；1.30(m,2H)；1.29(s,3H)；1.21(s,3H)；
example nos. 5-112: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.10(br s,1H)；7.99(d,2H)；7.94(2xd,2H)；1.63(m,4H)；1.15(m,7H)；0.85(m,1H)；
example nos. 5 to 115: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.09(br s,1H)；7.98(d,1H)；7.91(d,1H)；3.74(m,1H)；2.31(m,2H)；2.17(m,2H)；1.98(m,1H)；1.81(m,1H)；
example nos. 5-116: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.13(br s,1H)；7.98(d,1H)；7.92(d,1H)；3.32(m,1H)；1.93(m,2H)；1.77(m,2H)；1.67(m,2H)；1.58(m,2H)；
example nos. 5-117: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.11(br s,1H)；7.98(d,1H)；7.92(d,1H)；2.74(m,1H)；1.92(m,2H)；1.76(m,2H)；1.64(m,1H)；1.28(m,4H)；1.15(m,1H)；
example nos. 5-124: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.26(d,1H)；7.80(d,1H)；
example nos. 5-125: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.29(br s,1H)；8.18(d,1H)；8.06(d,1H)；6.97(t,1H)；
example nos. 5-126: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.08(d,1H)；7.65(d,1H)；6.73(t,1H)；2.65(s,3H)；
example nos. 5-127: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.89(br s,1H)；7.93(d,1H)；7.72(d,1H)；7.06(t,1H)；2.87(q,2H)；1.11(t,3H)；
example nos. 5-130: 1 H-NMR(400Mhz,CDCl 3 ):δ＝8.09(d,1H)；7.69(d,1H)；6.69(t,1H)；2.34(m,1H)；1.44(m,2H)；1.23(m,2H)；
example nos. 5-153: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.15(br s,1H)；7.95(d,1H)；7.90(d,1H)；2.67(s,3H)；
example nos. 5-155: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.10(br s,1H)；7.95(d,1H)；7.89(d,1H)；2.36(m,1H)；M 1.24(m,4H)；
example nos. 5-160: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.92(br s,1H)；7.84(d,1H)；7.75(d,1H)；7.07(t,1H)；2.57(s,3H)；
example nos. 5-161: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.89(br s,1H)；7.85(d,1H)；7.76(d,1H)；7.04(t,1H)；2.87(q,2H)；1.13(t,3H)；
example nos. 5-162: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.89(br s,1H)；7.85(d,1H)；7.77(d,1H)；6.96(t,1H)；2.35(m,1H)；1.24(m,4H)；
example nos. 5-187: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.55(br s,1H)；7.75(d,1H)；7.71(d,1H)；2.62(s,3H)；2.21(m,1H)；0.92(m,2H)；0.45(m,2H)；
example nos. 5-189: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝13.52(br s,1H)；7.75(d,1H)；7.71(d,1H)；2.44(m,1H)；2.16(m,1H)；1.18(m,4H)；0.92(m,2H)；0.48(m,2H)；
example nos. 5-201: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.12(br s,1H)；8.15(d,1H)；8.03(d,1H)；7.73(m,1H)；7.56(m,2H)；
example nos. 5 to 203: 1 H-NMR(400Mhz,DMSO-d 6 ):δ＝14.00(br s,1H)；8.04(d,1H)；7.96(d,1H)；6.71(dd,1H)；6.38(d,1H)；5.98(d,1H)。
B. formulation examples
a) The dusting agent is obtained by: 10 parts by weight of a compound of the formula (I) are mixed with 90 parts by weight of talc as inert substance and the mixture is comminuted in a hammer mill.
b) Wettable powders which are readily dispersible in water are obtained by: 25 parts by weight of the compound of the formula (I), 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting agent and dispersant are mixed and the mixture is ground in a pin-and-disk mill.
c) A dispersion concentrate which is readily dispersible in water is obtained by: 20 parts by weight of a compound of the formula (I) and 6 parts by weight of an alkylphenol polyglycol ether (C:)
Figure BDA0002379467770000861
X207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, from about 255 to above 277 c) and the mixture is ground in a ball mill to a fineness of less than 5 μm.
d) Emulsifiable concentrates were obtained from 15 parts by weight of the compound of formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
e) The water-dispersible granules are obtained by: mixing the following components:
75 parts by weight of a compound of the formula (I),
10 parts by weight of calcium lignosulfonate,
5 parts by weight of sodium lauryl sulfate,
3 parts by weight of polyvinyl alcohol, and
7 parts by weight of kaolin clay,
the mixture is ground in a pin-disk mill and the powder is granulated in a fluidized bed by spraying water as granulation liquid.
f) Water-dispersible granules can also be obtained by: the following components were homogenized and pre-comminuted in a colloid mill:
25 parts by weight of a compound of the formula (I),
5 parts by weight of sodium 2,2 '-dinaphthylmethane-6, 6' -disulfonate,
2 parts by weight of oleoyl methyl taurate,
1 part by weight of a polyvinyl alcohol,
17 parts by weight of calcium carbonate, and
50 parts by weight of water, based on the total weight of the composition,
the suspension is then ground in a sand mill and the resulting suspension is atomized and dried in a spray tower using a single-phase nozzle.
C. Biological examples
Abbreviations used herein represent:
Figure BDA0002379467770000871
Figure BDA0002379467770000881
D1 WO 2012/028579 A1
1. pre-emergence herbicidal action on harmful plants
Seeds of monocotyledonous or dicotyledonous weed plants and crop plants are placed in sandy loam in wood fibre pots and covered with soil. The compounds according to the invention, formulated as Wettable Powders (WP) or as Emulsifiable Concentrates (EC), are then applied to the surface of the covering soil in the form of an aqueous suspension or emulsion, at a water application rate equal to 600 to 800L/ha, with the addition of 0.5% of a wetting agent. After treatment, the pots were placed in a greenhouse and the greenhouse conditions were maintained under good growth conditions for the test plants. After a test period of 3 weeks, damage to the test plants was assessed visually by comparison with untreated controls (percent herbicidal activity (%): 100% activity = plant dead, 0% activity = same as control plants). Here, many of the compounds of the invention show an activity of at least 80% on a large number of important harmful plants at application rates of 320g per hectare or less.
In addition, certain substances are also harmless to dicotyledonous crops, such as soybeans, cotton, rape, sugar beet or potatoes. Some of the compounds of the invention show high selectivity and are therefore suitable for controlling unwanted vegetative growth in crops by the shoot front method. The data in tables B1 to B17 below show, in an exemplary manner, the preemergence herbicidal action of the compounds according to the invention, the herbicidal activity being expressed in percent.
Table B1: pre-emergence action on ALOMY
Figure BDA0002379467770000882
Figure BDA0002379467770000891
Figure BDA0002379467770000901
Figure BDA0002379467770000911
Table B2: pre-emergence effects on AVEFA
Figure BDA0002379467770000912
Figure BDA0002379467770000921
Figure BDA0002379467770000931
Figure BDA0002379467770000941
Table B3: pre-emergence action on CYPES
Figure BDA0002379467770000942
Figure BDA0002379467770000951
Figure BDA0002379467770000961
Table B4: pre-emergence effects on DIGSA
Figure BDA0002379467770000971
Table B5: pre-emergence effects on ECHCG
Figure BDA0002379467770000981
Figure BDA0002379467770000991
Figure BDA0002379467770001001
Figure BDA0002379467770001011
Figure BDA0002379467770001021
Table B6: pre-emergence action on LOLMU
Figure BDA0002379467770001022
Figure BDA0002379467770001031
Table B7: pre-emergence effects on LOLRI
Figure BDA0002379467770001032
Figure BDA0002379467770001041
Table B8: pre-emergence effects on LOLRI
Figure BDA0002379467770001042
Figure BDA0002379467770001051
Figure BDA0002379467770001061
Figure BDA0002379467770001071
Figure BDA0002379467770001081
Table B9: pre-emergence effects on ABUTH
Figure BDA0002379467770001082
Figure BDA0002379467770001091
Figure BDA0002379467770001101
Figure BDA0002379467770001111
Figure BDA0002379467770001121
Figure BDA0002379467770001131
Table B10: pre-emergence effects on AMARE
Figure BDA0002379467770001132
Figure BDA0002379467770001141
Figure BDA0002379467770001151
Figure BDA0002379467770001161
Figure BDA0002379467770001171
Figure BDA0002379467770001181
Table 11: pre-emergence action on MATIN
Figure BDA0002379467770001182
Figure BDA0002379467770001191
Figure BDA0002379467770001201
Figure BDA0002379467770001211
Figure BDA0002379467770001221
Figure BDA0002379467770001231
Table B12: pre-emergence action on PHPHPU
Figure BDA0002379467770001232
Figure BDA0002379467770001241
Figure BDA0002379467770001251
Table B13: pre-emergence action on POLCO
Figure BDA0002379467770001252
Figure BDA0002379467770001261
Figure BDA0002379467770001271
Table B14: pre-emergence action on STEME
Figure BDA0002379467770001272
Figure BDA0002379467770001281
Figure BDA0002379467770001291
Figure BDA0002379467770001301
Figure BDA0002379467770001311
Table B15: pre-emergence action on VIOTR
Figure BDA0002379467770001312
Figure BDA0002379467770001321
Figure BDA0002379467770001331
Figure BDA0002379467770001341
Figure BDA0002379467770001351
Figure BDA0002379467770001361
Table B16: pre-emergence action on VERPE
Figure BDA0002379467770001362
Figure BDA0002379467770001371
Figure BDA0002379467770001381
Figure BDA0002379467770001391
Figure BDA0002379467770001401
Table B17: pre-emergence action on HORMU
Figure BDA0002379467770001402
Figure BDA0002379467770001411
2. Post-emergence herbicidal action against harmful plants
Seeds of monocotyledonous or dicotyledonous weed plants and crop plants are placed in sandy loam in wood fibre pots, covered with soil and cultivated in the greenhouse under good growth conditions. The test plants were treated at the single leaf stage two to three weeks after sowing. The compounds of the invention, formulated as Wettable Powders (WP) or as Emulsifiable Concentrates (EC), are then sprayed onto the green parts of the plants in the form of aqueous suspensions or emulsions, at a water application rate equal to 600 to 800L/ha, with the addition of 0.5% of a wetting agent. After the test plants were placed in the greenhouse for about 3 weeks under optimal growth conditions, the effect of the formulations was assessed visually by comparison with untreated controls (percent herbicidal effect (%): 100% activity = plant dead, 0% activity = same as control plant). Here, many of the compounds of the invention show at least 80% activity on a large number of important harmful plants at application rates of 80g per hectare or less. At the same time, the compounds according to the invention, when applied post-emergence, do not cause visible damage to gramineous crops, such as barley, wheat, rye, millet/sorghum, maize or rice, even at high active ingredient doses. In addition, certain substances are also harmless to dicotyledonous crops, such as soybeans, cotton, rape, sugar beet or potatoes. Certain of the compounds of the present invention exhibit high selectivity and are therefore suitable for controlling unwanted vegetative growth in crops by post-emergence methods. The data in tables B18 to B34 below show, in an exemplary manner, the postemergence herbicidal action of the compounds according to the invention, the herbicidal activity being expressed as a percentage.
Table B18: post-emergence action on ALOMY
Figure BDA0002379467770001421
Figure BDA0002379467770001431
Table B19: post-emergence action on AVEFA
Figure BDA0002379467770001432
Figure BDA0002379467770001441
Figure BDA0002379467770001451
Table B20: post-emergence effects on CYPES
Figure BDA0002379467770001452
Figure BDA0002379467770001461
Table B21: post-emergence action on DIGSA
Figure BDA0002379467770001462
Figure BDA0002379467770001471
Table B22: post-emergence effects on ECHCG
Figure BDA0002379467770001472
Figure BDA0002379467770001481
Figure BDA0002379467770001491
Figure BDA0002379467770001501
Table B23: post-emergence effects on LOLMU
Figure BDA0002379467770001511
Table B24: post-emergence effects on LOLRI
Figure BDA0002379467770001512
Figure BDA0002379467770001521
Table B25: post-emergence action on SETVI
Figure BDA0002379467770001522
Figure BDA0002379467770001531
Figure BDA0002379467770001541
Figure BDA0002379467770001551
Table B26: post-emergence effects on ABUTH
Figure BDA0002379467770001552
Figure BDA0002379467770001561
Figure BDA0002379467770001571
Figure BDA0002379467770001581
Figure BDA0002379467770001591
Table B27: post-emergence effects on AMARE
Figure BDA0002379467770001592
Figure BDA0002379467770001601
Figure BDA0002379467770001611
Figure BDA0002379467770001621
Figure BDA0002379467770001631
Table B28: post-emergence action on MATIN
Figure BDA0002379467770001632
Figure BDA0002379467770001641
Figure BDA0002379467770001651
Figure BDA0002379467770001661
Table B29: post-emergence action on PHPHPU
Figure BDA0002379467770001671
Figure BDA0002379467770001681
Figure BDA0002379467770001691
Figure BDA0002379467770001701
Table B30: post-emergence action on POLCO
Figure BDA0002379467770001702
Figure BDA0002379467770001711
Figure BDA0002379467770001721
Table B31: post-emergence action on STEME
Figure BDA0002379467770001722
Figure BDA0002379467770001731
Figure BDA0002379467770001741
Figure BDA0002379467770001751
Figure BDA0002379467770001761
Figure BDA0002379467770001771
Table B32: post-emergence action on VIOTR
Figure BDA0002379467770001772
Figure BDA0002379467770001781
Figure BDA0002379467770001791
Figure BDA0002379467770001801
Figure BDA0002379467770001811
Table B33: post-emergence action on VERPE
Figure BDA0002379467770001812
Figure BDA0002379467770001821
Figure BDA0002379467770001831
Figure BDA0002379467770001841
Table B34: post-emergence effects on HORMU
Figure BDA0002379467770001842
3. Comparative experiment
The herbicidal activity of some of the compounds disclosed in WO2012/028579A1 on harmful plants by pre-and post-emergence methods was compared with that of the structurally closest compounds of the present invention. The data from these comparative experiments demonstrate the advantages of the compounds of the present invention.
TABLE V1 Pre-emergence
Figure BDA0002379467770001843
TABLE V2 Pre-emergence
Figure BDA0002379467770001844
Figure BDA0002379467770001851
TABLE V3 Pre-emergence
Figure BDA0002379467770001852
TABLE V4 Pre-emergence
Figure BDA0002379467770001853
TABLE V5 Pre-emergence
Figure BDA0002379467770001854
TABLE V6 Pre-emergence
Figure BDA0002379467770001855
TABLE V7 Pre-emergence
Figure BDA0002379467770001856
Figure BDA0002379467770001861
TABLE V8 Pre-emergence
Figure BDA0002379467770001862
TABLE V9 Pre-emergence
Figure BDA0002379467770001863
TABLE V10 Pre-emergence
Figure BDA0002379467770001864
TABLE V11 Pre-emergence
Figure BDA0002379467770001865
TABLE V12 Pre-emergence
Figure BDA0002379467770001866
TABLE V13 Pre-emergence
Figure BDA0002379467770001871
TABLE V14 post-emergence
Figure BDA0002379467770001872
TABLE V15 post-emergence
Figure BDA0002379467770001873
TABLE V16 post-emergence
Figure BDA0002379467770001874
TABLE V17 post-emergence
Figure BDA0002379467770001875
Figure BDA0002379467770001881
TABLE V18 postemergence
Figure BDA0002379467770001882
TABLE V19 post-emergence
Figure BDA0002379467770001883
TABLE V20 post-emergence
Figure BDA0002379467770001884
TABLE V21 post-emergence
Figure BDA0002379467770001885
Figure BDA0002379467770001891

Claims (10)

1. 3-acyl benzamides of formula (I)
Figure FDA0004058371380000011
Wherein the symbols and subscripts are defined as follows:
R X is represented by (C) 1 -C 6 ) -an alkyl group,
x represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) Alkyl, (C) 3 -C 6 ) -cycloalkyl, R 1 O、R 2 S(O) n Or R 1 O-(C 1 -C 6 ) -an alkyl group,
y represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) -alkyl or R 1 O、R 2 S(O) n ，
Z represents (C) 1 -C 6 ) Alkyl radicals, (C) 3 -C 6 ) -cycloalkyl, halo- (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 6 ) -alkyl-O- (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 6 ) alkyl-C (O), (C) 1 -C 6 ) alkyl-C (O) - (C) 1 -C 6 ) -alkyl, phenyl or heterocyclyl, wherein said heterocyclyl is selected from the group consisting of piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxetanyl, thienyl and furanyl; wherein the groups phenyl, heterocyclyl and (C) 3 -C 6 ) Cycloalkyl each bearing m substituents R 3 ，
R 1 Is represented by (C) 1 -C 6 ) -alkyl or halo- (C) 1 -C 6 ) -an alkyl group, which is,
R 2 is represented by (C) 1 -C 6 ) -an alkyl group,
R 3 represents halogen, (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 3 ) -alkyl-O-C (O), cyano or halo- (C) 1 -C 6 ) -an alkyl group,
m represents 0, 1,2, 3 or 4,
n represents 0, 1 or 2.
2. The 3-acylbenzamide of claim 1 wherein
R X Is represented by (C) 1 -C 6 ) -an alkyl group,
x represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) Alkyl radicals, (C) 3 -C 6 ) -cycloalkyl, R 1 O、R 2 S(O) n Or R 1 O-(C 1 -C 6 ) -an alkyl group,
y represents halogen, (C) 1 -C 6 ) -alkyl, halo- (C) 1 -C 6 ) -alkyl or R 1 O、R 2 S(O) n ，
Z represents (C) 1 -C 6 ) Alkyl radicals, (C) 3 -C 6 ) -cycloalkyl, halo- (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 6 ) -alkyl-O- (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 6 ) alkyl-C (O), (C) 1 -C 6 ) alkyl-C (O) - (C) 1 -C 6 ) -alkyl or phenyl, wherein the radicals phenyl and (C) 3 -C 6 ) Cycloalkyl each bearing m substituents R 3 ，
R 1 Is represented by (C) 1 -C 6 ) -alkyl or halo- (C) 1 -C 6 ) -an alkyl group,
R 2 is represented by (C) 1 -C 6 ) -an alkyl group,
R 3 represents halogen, (C) 1 -C 6 ) Alkyl radicals, (C) 1 -C 3 ) -alkyl-O-C (O), cyano or halo- (C) 1 -C 6 ) -alkyl radical，
m represents 0, 1,2, 3 or 4,
n represents 0, 1 or 2.
3. The 3-acylbenzamide according to claim 1 or 2 wherein
R X Is represented by (C) 1 -C 6 ) -an alkyl group,
x represents fluorine, chlorine, bromine, iodine, methyl, ethyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxymethyl, methoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylsulfanyl or ethylsulfonyl,
y represents chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, difluoromethyl, methylsulfanyl, methylsulfinyl, methylsulfonyl or ethylsulfonyl,
z represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, tert-butyl, methoxymethyl, chloromethyl, acetyl, 1-methylcyclopropyl, 2-methylcyclopropyl, (2, 2-dimethyl) cyclopropyl, (1, 2-dimethyl) cyclopropyl, 2-fluorocyclopropyl, (2, 2-difluoro) cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-thienyl, 2-furyl, phenyl, 4-methoxyphenyl, 4-chlorophenyl, (3-trifluoromethyl) phenyl, 3, 5-difluorophenyl, trifluoromethyl or difluoromethyl.
4. A herbicidal composition comprising at least one compound according to any one of claims 1 to 3 in admixture with formulation adjuvants.
5. A herbicidal composition according to claim 4, which comprises at least one further pesticidal active substance selected from the group consisting of insecticides, acaricides, herbicides, fungicides, safeners and growth regulators.
6. A method for controlling unwanted vegetation, characterized in that an effective amount of at least one compound of the formula (I) as claimed in any of claims 1 to 3 or a herbicidal composition as claimed in claim 4 or 5 is applied to the plants or the locus of unwanted vegetation.
7. Use of a compound of the formula (I) according to any one of claims 1 to 3 or a herbicidal compound according to claim 4 or 5 for controlling unwanted vegetation.
8. Use according to claim 7, characterized in that the compounds of the formula (I) are used for controlling unwanted vegetation in crops of useful plants.
9. The use according to claim 8, characterized in that the useful plants are transgenic useful plants.
10. A compound of formula (II)
Figure FDA0004058371380000031
Wherein the symbols and subscripts are defined as follows:
l represents chlorine, methoxy or hydroxy,
X 1 represents methyl, ethyl, cyclopropyl, methoxy, methylsulfanyl, ethylsulfanyl, fluorine, chlorine, bromine or iodine,
Y 1 represents a trifluoromethyl group or a difluoromethyl group,
z represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, a chloromethyl group, an acetyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a (2, 2-dimethyl) cyclopropyl group, a (1, 2-dimethyl) cyclopropyl group, a 2-fluorocyclopropyl group, a (2, 2-difluoro) cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-thienyl group, a 2-furyl group, a phenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a (3-trifluoromethyl) phenyl group, a (3, 5-difluoro) phenyl group, a trifluoromethyl group or a difluoromethyl group.
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